But she's still his wife.
Yeah, the union in the eyes of God carried extreme weight, even though it was only mere humans and paperwork (and lies) involved in it... I don't know where everyone got the idea that God loves ceremony and technicalities (which is all their marriage was) or legalities, above all else....
spoiler
It just struck me that in DS they like to imply thoughts or feelings on the parts of characters, without their ever being voiced. Someone here talked about Quentin's strange reaction to the Barnabas-Carl incident, how he seemed to just accept it, but maybe he was really scared of what Barnabas might do if he were to object. VW may very well have thought "Am I a witch?" for a moment, or any number of other things at different moments. Not every thought and feeling comes out in dialogue. Perople don't talk about every single feeling, apart from on modern American television.
All that Devil stuff with Angelique is problematic for me. That's of course how Christianity eliminated competing pagan religions, like Wicca (if that's a noun), by telling everyone they worked for the Devil. As soon as the Devil got involved in DS, we have his agents doing Bad for its own sake, not for recognizable, understandable human motives. That undercuts any drama.