Objective: Self-harm and personality psychopathology have been linked, with the most robust correlations existing between negative affectivity and self-harm. Psychological pain, an emotionally-based aversive feeling, has been linked to self-harm. Considering the connection between personality psychopathology and self-harm, psychological pain may enhance self-harm risk. Participants: Analyses were conducted on 525 undergraduate students in the Spring and Fall semesters of 2019. Methods/Results: Correlation analyses indicated that self-harm was moderately correlated with Negative Affectivity, Detachment, Antagonism, Disinhibition, and Psychoticism. Additionally, self-harm was correlated with psychological pain. When examining if psychological pain moderates the relation between personality psychopathology and self-harm, results were mixed. In the cases of Disinhibition and Psychoticism, psychological pain enhanced self-harm. There was no moderating effect on the relations with Negative Affectivity, Detachment, or Antagonism. Conclusions: These findings support the role of psychological pain in self-harm outcomes for those experiencing personality psychopathology; however, this varies depending on the maladaptive traits.