It could be the remaining Jedi. Since Luke has joined the dark side, the Jedi who still uphold the light side would be his natural antagonists. They would see him as a threat to all they stand for and would try to stop him from spreading the influence of the dark side. For example, Leia, if she still adheres to the Jedi teachings, would be in direct opposition to Luke.
A new dark side character could also be the main antagonist. This character might initially have been the one to lead Luke to the dark side, but then realizes that Luke's power and new - found dark side abilities are a threat to their own plans. So, they start to oppose Luke. Maybe this new character wants to use the dark side to rule the galaxy in a very specific and cruel way, and Luke has different ideas about how to use the dark side's power.
It could be the remaining Jedi. Since Luke is turning to the dark side, the Jedi who still uphold the light side values would be against him. They would see him as a threat to the balance they are trying to maintain and would try to stop him from fully embracing the dark side.
One possible plot could be that Luke is lured by the power the dark side offers. Maybe he gets frustrated with the slow progress of the light side in bringing order to the galaxy. He might see the Sith as more efficient in getting things done. For example, if the Republic is still facing numerous threats and the Jedi are tied by their code not to take extreme measures, Luke could be tempted to cross over.
Occasionally, comics depict Luke Skywalker having encounters or internal conflicts involving the dark side. But it depends on the specific comic storyline and context.
Perhaps a powerful dark side cult leader. They could manipulate Ezra into believing that their way is the right one and that the dark side is a misunderstood power. The cult leader might use Ezra's own insecurities and desires to draw him into the dark side.
It could be Hawk Moth. He might finally succeed in corrupting Adrien. Hawk Moth could use Adrien's inner doubts and fears to his advantage. For instance, if Adrien is worried about losing his loved ones, Hawk Moth could promise him a way to keep them safe if he joins the dark side.
One of the main themes could be the struggle between good and evil. Luke Skywalker is typically a symbol of the light side, so exploring his journey towards the dark side would likely involve his internal battle with his own moral compass. Another theme might be the allure of power that the dark side offers and how it can corrupt even the most noble of characters like Luke.
Palpatine could still be the main antagonist even if Luke turns to the dark side. He might try to use Luke as a more powerful weapon against any remaining Jedi or the Rebel Alliance. Palpatine would see Luke's newfound dark side power as a means to further his own control over the galaxy.
Luke's friends from the light side could also be important. Characters like Leia, Han Solo, or Chewbacca. Their reactions to Luke's turn and their attempts to bring him back would be significant aspects of the story. There could also be new characters created specifically for this novel, perhaps some Jedi who were thought to be dead but are actually in hiding and oppose Luke's new path.
It could be the remaining Jedi. Since Rey is turning, the Jedi who still uphold the light side would see her as a threat. They would try to stop her from causing more harm with her newfound dark side powers.
If Luke joins the Dark Side, it would completely change the dynamic of the Star Wars universe. His friends would be shocked and heartbroken. Leia, for instance, would probably try to bring him back. The Rebellion would lose a great hope and the Empire might gain an unexpected and powerful ally. It could also lead to a different kind of struggle within the galaxy as those who once believed in Luke now have to face him as an enemy.