This study used latent variable mixture modeling (LVMM) with a combined sample of undergraduates and internet users who endorsed non-suicidal self-injury (NSSI; N = 440) to identify profiles of non-suicidal self-injurers. LVMM results revealed four distinct subtypes (“Experimental NSSI,” “Mild NSSI,” “Multiple Functions/Anxious,” and “Automatic Functions/Suicidal” groups) that were similar to those found in a prior study of undergraduates Klonsky and Olino (Journal of Consulting and Clinical Psychology 76:22-27, 2008), with an additional fifth “Multi-method.” ANOCOVAs and logistic regressions showed the first four groups differed on aspects of psychopathology in a similar fashion to the previous study. Specifically, the Experimental and Mild NSSI groups had the lowest levels of psychopathology, and the AF/Suicidal group had higher levels of psychopathology than the first three groups except for anxiety, which was higher for the MF/Anxious group. The additional Multi-method group was found to have higher levels of psychopathology than all other groups, but not significantly different from the MF/Anxious group. With regard to alcohol use and drinking motives, the MF/Anxious group had the highest level of hazardous drinking and drinking motives related to coping with depression and anxiety, enhancement, and conformity. The other four groups were not differentiated from one another on any drinking variable. Findings suggest that NSSI may be better conceptualized as a heterogeneous syndrome in clinical and research settings, with one sub-group being more at-risk for hazardous alcohol use.