Recent research found that drinking alcohol mixed with energy drinks (AmED) could be riskier than drinking alcohol alone. Our aim was to compare rates of risk behaviors in consumers of AmED versus exclusive alcohol drinkers, matching them based on their drinking frequency. Data about 16-year-old students who reported the number of occasions on which they had drunk AmED or alcohol only in the preceding 12 months (n = 32,848) were drawn from the 2019 ESPAD study. After matching for consumption frequency, the sample consisted of 22,370 students (11,185 AmED consumers and 11,185 exclusive alcohol drinkers). Key predictors comprised substance use, other individual risk behaviors, and family characteristics (parental regulation, monitoring, and caring). The multivariate analysis showed significantly higher odds of being AmED consumers compared to being exclusive alcohol drinkers in the majority of the investigated risk behaviors, including: daily tobacco smoking, illicit drug use, heavy episodic drinking, truancy at school, engaging in physical fights and serious arguments, having troubles with the police, and having unprotected sexual intercourse. Instead, lower odds were found for reporting high parents' educational level, medium and low family economic status, perceived possibility to freely talk about problems to family members, spending free time reading books or other hobbies. Our study shows that, given the same consumption frequency in the past year, AmED consumers typically reported higher associations with risk-taking behaviors compared to exclusive alcohol drinkers. These findings advance past research that failed to control for the frequency of AmED use versus exclusive alcohol consumption.