Astarion can be found standing on a road west of the crashed Nautiloid in the Wilderness. When found, a scene will play where he is looking for help in defeating an Intellect Devourer. Afterwards, he can be asked to join the party.
Background
Astarion prowled the night as a vampire spawn for centuries, serving a sadistic master until he was snatched away. Now he can walk in the light and has the chance at a new life, but how long can he keep his past buried?
Personality
Astarion has a sadistic personality and often approves of evil, cruel or egotistic actions, though he seems to accept certain pragmatic ones. He values hedonism. He is disdainful, but not hostile, towards those he considers weak and unworthy of his attention.
Interactions
Approval
Astarion likes displays of power and cruelty. He enjoys it when the player mocks others.
The following story and dialogue choices will cause Astarion to gain approval.
After killing Auntie Ethel's true form, use the wand to resurrect Mayrina's dead husband Connor, give her the wand, then tell Astarion that it was funny
Blighted Village
Deliver the final blow to the goblin Fezzerk
Goblin Camp
Deceive the goblins, say 'you can't be serious', then fling poo at them
Say 'Boo' to Volo as he performs
Tell Tracker Grikka (or another goblin NPC) that you will "get answers for them" when discussing their prisoners.
Agree to Abdirak's ritual for Loviatar
Tell Torturer Spike in the goblin camp that you will torture the prisoner
Tell Priestess Gut in the goblin camp that you're here to kill her
Remove the ring from Crusher's foot after you kneel in front of him.
Agree to Abdirak's endure teachings on Loviatar's love.
Turn down the druid Halsin's request to help the grove in favor of saving yourself first.
Camp
In camp on the first night, tell Shadowheart to remain cautious.
Decline Raphael's offer to remove the tadpole.
Tell him that you are not the devil's plaything in regards to Raphael's offer.
Kill Yurgir and talk to Raphael about it, then promise Astarion you'll help him kill Cazador
Disapproval
Astarion dislikes displays of weakness and does not like acts of kindness or charity that offer no reward. He disapproves when the player tries to reign him in or restrict him in some way.
The following story and dialogue choices will cause Astarion to lose approval.
Spoiler warning! This section reveals details about the story of Baldur's Gate 3.
After the Party, with at least medium approval, Astarion will ask the player if they want to "have some fun". If the player accepts, they will meet with Astarion in the woods. They will embrace and kiss, and Astarion will push the player into a tree, showing his teeth. The player can demand Astarion to hide them or give in. The lovers will fall into the ground and a sexual scene will occur.
When the player awakes the next morning, they will notice scars on Astarion's back.