In the 'dear villainous husband novel', the main characters are likely centered around the villainous husband himself. He could be a character with a dark past or motives that make him seem villainous. Then there would probably be a counterpart, like a female character who is either his love interest or the one who challenges his villainous ways. There could also be other characters like servants or rivals who add more depth and complexity to the story, by either fueling the husband's villainy or trying to expose it.
Typically in a novel like this, there would be the titular villainous husband. He could be a powerful man, perhaps a lord or a wealthy businessman. There would also likely be a female protagonist, who could be an innocent young woman who was forced into a relationship with the villainous husband. There might also be supporting characters like friends or family members of the main characters who play important roles in the story, either helping or hindering the relationship between the two main characters.
Since I haven't read it, I'm not sure. But it might have a villainous husband as one of the main characters, and probably a female lead who is somehow connected to him, maybe his wife.