Abstract: Background and Aims Dysfunction in brain regions underlying impulse control, reward processing and executive function have been associated previously with adolescent alcohol misuse. However, identifying pre‐existing neurobiological risk factors, as distinct from changes arising from early alcohol‐use, is difficult. Here, we outline how neuroimaging data can identify the neural predictors of adolescent alcohol‐use initiation and misuse by using prospective longitudinal studies to follow initially alcohol‐naive individuals over time and by neuroimaging adolescents with inherited risk factors for alcohol misuse. Method A comprehensive narrative of the literature regarding neuroimaging studies published between 2010 and 2016 focusing on predictors of adolescent alcohol use initiation and misuse. Findings Prospective, longitudinal neuroimaging studies have identified pre‐existing differences between adolescents who remained alcohol‐naive and those who transitioned subsequently to alcohol use. Both functional and structural grey matter differences were observed in temporal and frontal regions, including reduced brain activity in the superior frontal gyrus and temporal lobe, and thinner temporal cortices of future alcohol users. Interactions between brain function and genetic predispositions have been identified, including significant association found between the Ras protein‐specific guanine nucleotide releasing factor 2 (RASGRF2) gene and reward‐related striatal functioning. Conclusions Neuroimaging predictors of alcohol use have shown modest utility to date. Future research should use out‐of‐sample performance as a quantitative measure of a predictor's utility. Neuroimaging data should be combined across multiple modalities, including structural information such as volumetrics and cortical thickness, in conjunction with white‐matter tractography. A number of relevant neurocognitive systems should be assayed; particularly, inhibitory control, reward processing and executive functioning. Combining a rich magnetic resonance imaging data set could permit the generation of neuroimaging risk scores, which could potentially yield targeted interventions.