The functions of nonsuicidal self-injury (NSSI) consist of social and emotional aspects (Social influence, Sensation seeking, Internal and External emotion regulation). Previous studies have indicated that dysfunction in reward-related brain structures especially the striatum might drive this habitual behavior. However, no studies to date have investigated the associations between striatum and different functions for adolescents engaging in NSSI behaviors. Here, we recruited 35 depressed adolescents with recent NSSI behaviors and 36 healthy controls and acquired structural brain images, depressive symptoms, social, academic and family environments assessments, in addition to NSSI functions in patients only. Subcortical volumes and cortical thickness were estimated with FreeSurfer. Mixed linear regressions were performed to examine associations between striatal structures (caudate, putamen, nucleus accumbens, pallidum) and NSSI functions, with age, sex, total intracranial volume, hemisphere and depression severity included as covariates. Effect of environmental factors and potential associations with cortical thickness and other subcortical volumes were also tested. We found that, among the four functions, external emotional regulation represented the main function for NSSI engagement. Increased external emotion regulation was significantly associated with smaller putamen volume. No environmental factors biased the association with putamen. No associations with other cortical or subcortical regions were observed. Our findings suggested that smaller putamen might be a biomarker of NSSI engagement for depressed adolescents when they regulated frustrated or angry emotions. The results have potentially clinical implications in early identification and brain intervention of NSSI in youth.