I'm really confused. Was he under a spell or not? It seemed pretty clear that Gothel spelled him until they kidnap Hook and it seems like he's freely with them from then on out. Hook even says something "You're a disgrace to your badge."
My best guess: She spelled him to get him out of the police station, then told him her whole plan (and possibly woke him up, if he has a fairy tale counterpart) and offered him a chance to live just like she offered Regina.