Psychological pain is a significant risk factor for suicidality across several populations, including among undergraduates and individuals with depression. Chronic physical pain is also associated with increased risk for suicidality, and neuroimaging research suggests that psychologically painful experiences (i.e., rejection, loss) activate neural systems that are involved in physical pain. Despite these overlaps, psychological pain has not previously been examined among individuals with chronic pain. In the current study, we performed a psychometric analysis of a commonly used assessment of psychological pain in a sample of individuals with and without chronic pain. Confirmatory factor analyses and tests of measurement invariance were used to assess the hypothesized one-factor structure of the Psychache Scale and its relationship to depression and pain catastrophizing across individuals with and without chronic pain. Undergraduates (N = 724) completed the study, 100 of whom reported chronic pain lasting for at least 3 months (Mean duration of pain = 37 months). Results indicated that psychological pain, depression, and pain catastrophizing each loaded onto unique factors that were significantly positively correlated with one another. The model was invariant across the two groups, and individuals with chronic pain reported elevated levels of psychological pain, depression, and pain catastrophizing. These results indicate that the Psychache Scale may be a valuable tool for assessing the psychological component of chronic pain syndromes.