Non-suicidal self-injury (NSSI), of which the predisposing factors are complex and diverse, profoundly affects the physical and mental health of young people. Therefore, this work established an NSSI intermediary network model considering the interaction of multiple factors. A mediating effect between attention-deficit/hyperactivity disorder (ADHD) and NSSI, considering the influence of comorbidities, such as depression, anxiety, and impulsive personality, was proposed based on sex differences. A total of 2,689 middle school students in Ningbo City, Zhejiang Province, China, were randomly sampled and participated in this study. Data regarding their demographic characteristics, attention deficit, hyperactivity/impulsivity, NSSI, anxiety, depression, internet addiction, and other comorbid symptoms were collected and analyzed. After initially screening the data, variables were assessed for significance using a single-factor inter-group difference analytic method, and a binary logistic regression analysis was performed. The intermediary effect of factors influencing NSSI in males and females was also analyzed. The overall NSSI rate was 15.16%. The results showed that the impact of individual impulsivity characteristics (impulsiveness, the ADHD with hyperactivity/impulsivity subtype) on NSSI behavior was not significant (regression results, P>0.05). The degree of association between ADHD with attention deficit and ADHD with comprehension deficit subtypes, and other comorbid symptoms (depression, anxiety, and internet addiction disorder) and NSSI, with odds ratios (ORs) of 7.6/6.42/436.68/3.82/1.86, and 95% bootstrap confidence intervals (CIs) of 4.64, 12.87/3.46, 12.67/137.42, 2659.13/2.32, 6.37/1.31, 2.82, respectively. The results also showed significant effects of ADHD subtypes on comorbid symptoms and the path effects of NSSI (P<0.01). Among them, the mediating effect was the strongest when anxiety was the mediating variable, and the mediating effect of girls was higher than that of boys. The results of this work demonstrated the influence of ADHD symptoms on NSSI behavior. Among patients with ADHD, patients with subtypes with obvious attention deficit characteristics were more likely to exhibit NSSI behavior, whereas the hyperactive impulse subtype had no direct impact on NSSI. We conclude that adolescent impulsivity may not be directly related to NSSI behavior and that impulsive characteristics jointly affect NSSI behavior through a series of NSSI comorbid symptoms. Notably, the probability of symptom onset and the degree of comorbidity was significantly higher in girls than in boys of the same age, and girls were more prone to NSSI behavior. These findings provide effective theoretical support for the prevention and treatment of adolescent NSSI behavior.