Early adolescent drinking has been identified as an important risk factor for the development of alcohol dependence. Both perceived peer drinking and personality profiles have been implicated as risk factors for early adolescent drinking. However, research is yet to determine how these 2 factors may interact to increase such risk. This study aimed to determine whether personality profiles moderated the relationship between perceived peer drinking and early adolescent drinking. Baseline data were utilized in the analyses, from 3,287 adolescents (Mage = 13.51 years, SD = .58; 54% female; 78% born in Australia) participating in the Climate Schools Combined Study (a cluster randomized controlled trial with 75 schools located across Queensland, New South Wales, and Western Australia, Australia). Lifetime consumption of alcohol, perceived peer drinking, and personality profiles (Substance Use Risk Profile Scale) were measured. A moderated binary logistic regression found the personality profiles of impulsivity, sensation seeking, and hopelessness were positively related to early adolescent drinking, whereas anxiety sensitivity had a negative association. A significant interaction revealed that adolescents with higher levels of sensation seeking and who perceived their peers to be drinking were significantly more likely to report early adolescent drinking (consumption of a full standard drink; OR = 1.043; 95% CI [1.018–1.069]). These results indicate that perception of peer drinking is more strongly associated with early adolescent drinking, when adolescents are also high on sensation seeking. Prevention and intervention programs could consider targeting both sensation seeking and perceived peer drinking in adolescents.