Magnus
Warrior
None
One of the 4 Heroes unlocked by default
Andrin
Scout
None
One of the 4 Heroes unlocked by default
Evelyn
Mage
None
One of the 4 Heroes unlocked by default
Reginald
Healer
None
One of the 4 Heroes unlocked by default
Heiner
Warrior
Velkarath in either Act 2 or Act 3
Interact with the Crumbling Tower "The Last Sentinel" in Senenthia and find Heiner's body without its core. [Accept] the Quest to find a new core somewhere in Velkarath. Once in Velkarath go to The Black Forge "The Gates of Black Forge" Map Node and select the [Enter] option. Next, [Combat] the two Golems (and a Fire Elemental if the Group Event before the combat fails) and win. Loot the rewards and the party should find a new Golem Core and the "Heiner Unlocked" dialog will pop up. No need to go 'plug the core in' to the empty Heiner in Senenthia, the game won't make things that tedious.
Thuls
Scout
Aquarfall Marsh in either Act 2 or Act 3
Interact with the Water Mill "Whispers In The Shadow" Map Node in Senenthia. Next, [Accept] Thul's Quest to find a very strong Venom which he mentions is likely in his homeland called Aquarfall Marsh, in a cave full of spiders. Once in the Marsh take whichever path feels 'right' and leads to the Spider Lair "The Spiders Cave" Map Node in the far south of the map. Be aware that one path does require about 800 Gold for a boat to get across. [Enter] the sub-dungeon, either the safe way or not, and get to the end of it (potentially grabbing the adorable Slimy along the way) to fight against the Spider Queen. Once defeated, the Queen's Venom should be part of the Loot, and the prompt for "Thuls Unlocked" should pop up.
Cornelius
Mage
Velkarath in either Act 2 or Act 3
Talk to Cornelius at the River Bridges "The Wandering Wizard" Map Node event in Senenthia. [Accept] his offer to find his magic staff and he mentions that his staff is likely with the old group he used to run with and is in their main base in Velkarath. Once in Velkarath go along bottom-type paths until you reach the Cult Temple "The Burning Hand" Map Node. Beat the boss of the Cultists, get the staff, and the "Cornelius Unlocked" dialog will appear.
Ottis
Healer
Just Senenthia
Find Ottis at the Isolated Chapel "The Scared Pigman" Map Node in Senenthia. [Accept] the Quest to defeat Yogger to give Ottis some peace of mind. Yogger is found at the Bandit Camp "Fresh Meat!" Map Node. After beating Yogger the "Ottis Unlocked" should pop up. It'll be interesting to see who takes Yogger's spot here when he's part of the player party after being unlocked in the Wolf Wars DLC.
Grukli
Warrior
Aquarfall Marsh in either Act 2 or Act 3
Interact with the Small Lake "The Fishing Contest" Map Node and select any option other than [Leave] for the event. However, if Andrin is in the party, his option guarantees to get the Fish regardless of how it works out. Then, hold on to this Fish until you get to Aquarfall Marsh and head toward the Waterfall Ledge "The Hungry Dwarf" Map Node. Both ways to get here involve taking a Ferry so save up about 800 Gold in advance or help the Crocomen to get the boat for free. Once at Grukli's event, give him the Fish, and the "Grukli Unlocked" should appear.
Sylvie
Scout
Faeborg in either Act 2 or Act 3
Before finding Sylvie, players need to go to the Forest Glade "The Moon Ritual" Map Node, [Combat] the Dryad, and [Wait] until the Moonstone cools down enough to pick it up. Then, go to Faeborg and travel to the Owl Guardian "The Depleted Guardian" Map Node to interact with Sylvie, give her the Moonstone, and "Sylvie Unlocked" will pop up.
Wilbur
Mage
Velkarath in either Act 2 or Act 3 and then The Void
Interact with the Rest Area "Knowledge For A Dream" Map Node in Velkarath to talk to Wilbur and [Accept] his quest to find a book about ancient technology. Then, in The Void of Act 4, go to The Library "The Ancient Library" Map Node on the first map and pick the [Continue] option to get his book there which gives the "Wilbur Unlocked" popup.
Malukah
Healer
Aquarfall Marsh in either Act 2 or Act 3
Start this quest by interacting with the Suspicious Hatch "The Hatch" Map Node in Senenthia. Jumping on the hatch (the [Enter] option) will guarantee the party gets into the Sub-Dungeon, while [Open] has a loss condition where they don't enter. Once inside, continue onward until the party is there once the "Lord of the Imps" Belphyor is summoned. Only pick the [Combat] option, as the other two lead to different rewards that aren't needed to unlock Malukah. Once players get Belphyor's Horn from his body, they can continue to the Aquarfall Marsh. In the Marsh map, the party has to take a "ferry" across the water at North Pier "Crocomen Mafia" map node for about 1000 Gold. After buying the boat, go to Malukah's Map Node and give her Belphyors Horn. After this, "Malukah Unlocked" should appear and players will also be able to pick some items from her shop as well.
Bree
Warrior
Faeborg in either Act 2 or Act 3 and then The Void
To start this quest, players need to pick Faeborg as either their Act 2 or Act 3 map. Once there, take the top patch to reach Bree at the Grove "Saving The Treants" event. She asks the party to find a place to plant Ylmer's Seed and players need to [Accept]. Then once in the second map (after the dual Guardian fight) of Act 4, head up the top path to the Garden "Sacred Garden" Map Node and select the [Dig] option. Right after this, "Bree Unlocked" should appear.
Gustav
Scout
Aquarfall Marsh for Act 2 then Faeborg for Act 3
To unlock Gustav, players must select Aquarfall as their Act 2 and Faeborg as their Act 3. In Aquarfall Marsh, they'll need to pay for the boat at the South Pier to reach the Lonely Rock "The Sad Minstrel" Map Node. There, Gustav will ask the party to get him a new Lute as his last one was broken by Crocomen. [Accept] this quest and head to Faeborg. Once there make sure to go along the bottom path toward the Faeborg Dragon boss, as this leads to the Mansion "Maniac Mansion" Map Node. In this event, select the [Continue] option and get Gustav's new Lute. Once obtained, the "Gustav Unlocked" should appear.
Zek
Mage
Faeborg in either Act 2 or Act 3
Zek's unlock quest starts in Senenthia at the Main Road "A Grave On The Road" Map Node. Depending on who is in the party, there will be character-specific options for this event, these work as well as the [Profane] option, just don't pick [Leave]. There is a secondary event "The Eerie Chest" that can happen here with a box, but regardless of how that turns out (if it appears), players should get a Strange Key. Take this key all the way to Faeborg in either Act 2 or Act 3 and go to the Sewer Outlet "The Exiled" Map Node and give Zek the key. And, just like that, "Zek Unlocked" will appear.
Nezglekt
Healer
Velkarath in either Act 2 or Act 3 and then The Void
This relatively long Across the Obelisk character unlock quest starts in Senenthia's Riverside Camp "The Stargazer" Map Node first map (which won't always appear). At this camp, either the [Ask] or [Pay] options work, and after the Divination Nezglekt will tell the player to talk to his brother in Velkarath. Go to Velkarath in either Act 2 or Act 3 and he'll be at the Campsite "Express Delivery" Map Node. After talking to him, Nezglekt's brother will ask the player if they can deliver a heavy package for him. The player must then pick which of their party member's "Potion" slot gets taken up by this Heavy Package, and they must keep it on them until the delivery is completed. Hold onto this Package until Act 4, The Void, and take it to the Airship "Tsnemo's Merchant Ship" Map Node. After delivering it, "Nezglekt Unlocked" should appear, which signals this character has been unlocked.
Yogger
Warrior
Wolf Wars DLC Expansion
A very simple unlock, in the first Act, just reach the Forest (Yogger's Diary) node on the upper part of the map right after the actual Yogger battle. Then, select the [Continue] Option here to enter the Wolf Wars DLC area. Progress through this DLC, until it takes the player back to normal Act areas. Then, complete a run as usual to see the Yogger character unlock.
Navalea
Warrior
Sands of Ulminin DLC Expansion
Complete Act 1 like Normal, then when choosing the next Act, choose the '[Continue] Cross the yellow portal from which dry and dusty air comes out'. This is the map players have access to in the Sands of Ulminin DLC. Once here, head to the Information Broker Common Event node relatively close to the starting town. Here, select the '[Pay] You pay 300g and ask about the sealed tomb in the north' option (make sure to have at least 300g on hand). Then, head up to the Tomb Common Event node near the top of the map. Choose either the [Enter] Option or any of the character-specific options (less chance of success). In the tomb, players should see Navalea's node on the Burial Chamber Character Event node. Pick the [Accept] option here, then head to the Mural node on the Tomb map. Here, select the [Continue] Option then continue however desired until Act 4. Complete the bottom floor of Act 4 and then on the next floor navigate the path that leads to the Cathedral Character Event on the top left of the map. Here there should only be one option, and after selecting it Navalea should be unlocked.
Laia
Paladin
Sands of Ulminin Expansion
Complete Act 1 like Normal, then when choosing the next Act, choose the '[Continue] Cross the yellow portal from which dry and dusty air comes out'. This is the map players have access to in the Sands of Ulminin DLC. Once players are here, they should see Laia's face on the map near the Side Pyramid Character Event node. At this node, pick the [Accept] option and continue however desired until Act 4. Complete the bottom floor of Act 4 and then on the next floor navigate the path that leads to the 'Battlefield' Character Event node in the bottom right. Pick the only option here, and Laia's task is complete and the 'Laia Unlocked' popup should appear.