Adolescent e-cigarette use has been labeled an epidemic and alcohol use during this developmental period is associated with deleterious outcomes. Though specific temperamental dimensions have been shown to predict substance use, profiles of temperament have rarely been examined as predictors. This study examines dimensions and profiles of adolescent temperament as predictors of early use of e-cigarettes and alcohol. The sample was comprised of adolescent (62.07% female, 87.59% White, 82.76% Hispanic/Latinx)/caregiver dyads (N = 146) who completed the first two timepoints (M age at second timepoint = 16.16, SD = 0.68) of a longitudinal adolescent substance use study. Models showed parent-reported effortful control predicted protection against adolescent use of e-cigarettes, whereas adolescent report of effortful control predicted protection against alcohol use. Though dissimilar in temperamental pattern, three profiles emerged from both parent- and adolescent-report-based latent profile analysis models. Adolescents characterized by parents as displaying a Resilient profile had greater odds of e-cigarette use than those characterized by a Reserved profile, whereas adolescents who self-characterized as Mixed-type had markedly greater odds of alcohol use than those who self-characterized as Resilient. Utilization of temperamental profiles may aid in identification of particularly vulnerable subgroups of adolescents who may benefit from relevant preventative programing.