The adverse impact of bullying and victimization on substance use among youth has received increasing attention. Bullying is a specific type of aggressive behavior that not only involves bullies and victims but also followers, who actively support or reinforce the bully; defenders, who intervene to defend or assist the victim; or outsiders who passively observe or ignore the bullying. Limited research to date has linked these five bullying role behaviors to substance use. The aim of this study was to investigate the relationship between each of the bullying role behaviors and adolescent alcohol and tobacco use. Participants were 1255 (748 female) students (Mage = 15.3, age range: 13-17 years) in Grades 9 (n = 714) and 11 (n = 541). Bullying role behaviors, alcohol and tobacco onset and intensity, and alcohol-related harms were assessed. Results revealed an association between pro-bullying behavior (bullying and following) and all substance use variables, and between defender behavior and smoking and alcohol-related harm. No relationship between victimization, or outsider behavior, and substance use was found after controlling for the other bullying roles. The findings highlight the complex relationship between bullying roles, alcohol and tobacco use and alcohol-related harm in adolescents.