This study investigated the extent to which adolescent social network positions are associated with the risk of lifetime daily smoking and nicotine dependence (ND), and whether these associations differ by gender. Using data from the National Longitudinal Study of Adolescent to Adult Health (N = 6,267), this study estimated multinomial logistic regression models. An increase in in-degree nominations, out-degree nominations, and Bonacich centrality was associated with a lower relative risk of never smoking daily versus ever smoking daily. By contrast, adolescents with greater in-degree nominations, out-degree nominations, Bonacich centrality, and network reach in three steps were at decreased risk for lifetime ND. Gender-stratified models indicate that the negative association between network position and never smoking daily was driven largely by women, whereas the positive association between network position and lifetime ND was driven largely by men. Incorporating social network structural approaches into adolescent smoking prevention efforts may be beneficial.