Volunteering can serve as a protective factor against substance abuse. Yet, it is unclear whether volunteering in specific community organizations, such as emergency services, promotes or protects against substance use. We aimed to (1) describe community volunteering characteristics among adolescents; (2) investigate differences in the prevalence of substance use according to community volunteering type; and (3) determine whether volunteering type was a predictor of substance use. We analyzed data from the 2018-2019 Health Behavior in School-aged Children survey among Israeli adolescents aged 11-17 years (N = 3972). Most participants (N = 2452; 61.7%) did not volunteer at all, 27.1% (N = 1077) volunteered in youth movements/councils, and 11.2% (N = 443) volunteered in community emergency services. In comparison to the emergency services group, there was a higher volunteering frequency among the youth movements/councils group. Of the three groups (nonvolunteering, volunteering in youth movements/councils, and volunteering in community emergency services), those in the community emergency services group reported a significantly higher prevalence of weekly alcohol use, lifetime cannabis use, and new psychoactive drug use, while no significant between-group differences were observed in smoking tobacco prevalence. Volunteering in the community emergency services has been linked to substance use, requiring the development of intervention programs by the school staff, before their active volunteering (e.g., guidance on emotional stress and substance abuse). Also, teachers can act as a protective factor for students, and identify emotional distress and anxiety in their students to prevent substance abuse. Furthermore, emergency services workers and instructors should also be aware of the higher risk of substance use among volunteering youth and should be given tools to better collaborate with parents and teachers in dealing with it.