Sensation seeking (SS) and impulse control (IC) are constructs at the core of dual systems models of adolescent risk taking. Using data from the National Longitudinal Study of Adolescent to Adult Health, age‐varying associations between SS and IC (predictors) and both any smoking in the previous 30 days and daily smoking (outcomes) were examined. The association between SS and both any smoking in the previous 30 days and daily smoking was strongest during adolescence. IC was consistently associated with any smoking in the previous 30 days and daily smoking, with the strongest association emerging during the mid‐20s to early 30s. The results provide a nuanced perspective on when the components of dual systems models may be most related to smoking.