Psychopathy is one of the most researched risk factors for violence. Yet, research in women is sparse. The present study aimed to test if the link between the four-facet structure of psychopathy and interpersonal violence and aggression was moderated by neurobiological function (indexed by resting respiratory sinus arrhythmia; RSA). Results showed the lifestyle and affective facets were associated with reactive aggression and these associations were moderated by low resting RSA. The interpersonal, affective, and antisocial facets were associated with proactive aggression but no moderation effect was found. The affective and antisocial facets of psychopathy were associated with histories of interpersonal violence, however, only the affective facet was moderated by low RSA. This is the first study in young women to demonstrate the link between affective psychopathic traits and interpersonal violence and reactive aggression is via aberrant prefrontal cortex functioning.