BackgroundResearch has shown an increased risk for Non-suicidal self-injurious (NSSI) behavior as well as Problematic Smartphone Use (PSU) and particularly in adolescence, a developmental period defined by multi-level changes and still poor self-control capacities associating with risk-taking behaviors. ObjectiveThe current study was aimed to assess the pattern of mutual relations characterizing NSSI considering self-control, internalizing and externalizing problems, and investigating how PSU fits within the network since NSSI and PSU are here conceptualized as attempts at emotion regulation. Age and gender differences were also assessed. MethodParticipants were Italian adolescents presenting NSSI behavior (N = 155; Mage = 14.68; SD = 1.647; Range = 11–18; 43.2%-females); the sample is based on community recruitment. A Network Analysis was performed to assess the organizational structure of NSSI; age and gender differences were assessed through multivariate rank tests further applying multiplicity control. ResultsThe emerged Network showed the centrality of low self-control and internalizing problems for NSSI. NSSI and PSU were associated through low self-control, and so were PSU and externalizing problems. Significant age differences were observed showing a decrease in NSSI as age increases (stat = −2.86; adj.p = .029). No gender differences have emerged. ConclusionsThe current findings provide support for the consideration and investigation of PSU as regards NSSI behavior in adolescence. Moreover, these findings point to the relevance of prevention practices during this peculiar developmental period, particularly sustaining self-control capacities and the use of more adaptive emotion regulation strategies, thereby limiting the accrue of at-risk behaviors.