Theoretical and empirical work suggests that aggression in those with borderline personality disorder (BPD) occurs primarily in the context of emotional reactivity, especially anger and shame, in response to perceived rejection. Using intensive repeated measures, we examined a within-person process model in which perceived rejection predicts increases in aggressive urges and behaviors via increases in negative affect (indirect effect) and in which BPD symptoms exacerbate this process (moderated mediation). Participants were 117 emerging adult women (ages 18–24) with recent histories of aggressive behavior who were recruited from a community-based longitudinal study of at-risk youth. Personality disorder symptoms were assessed by semistructured clinical interview, and aggressive urges, threats, and behaviors were measured in daily life during a 3-week ecological momentary assessment protocol. Multilevel path models revealed that within-person increases in perceived rejection predicted increases in negative affect, especially in women with greater BPD symptoms. In turn, increases in negative affect predicted increased likelihood of aggressive urges or behaviors. Further analysis revealed that BPD symptoms predicted greater anger and shame reactivity to perceived rejection, but not to criticism or insult. Additionally, only anger was associated with increases in aggression after controlling for other negative emotions. Whereas BPD symptoms exacerbated the link between perceived rejection and aggression via increases in negative affect (particularly anger), this process was attenuated in women with greater antisocial personality disorder symptoms. These findings suggest that anger reactivity to perceived rejection is one unique pathway, distinct from antisocial personality disorder, by which BPD symptoms increase risk for aggression.