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E-cigarette use by adolescents has been related to onset of cigarette smoking but there is little knowledge about the process(es) through which this occurs. Accordingly, we tested the role of cognitive and social factors for mediating the relation between e-cigarette use and smoking onset. A school-based survey was conducted with a baseline sample of 2,338 students in Hawaii (9th and 10th graders, mean age 14.7 years) who were surveyed in 2013 (Time 1, T1) and followed up 1 year later (Time 2, T2). We assessed e-cigarette use, cigarette smoking, demographic covariates, and 4 hypothesized mediators: smoking-related expectancies, prototypes, and peer affiliations as well as marijuana use. The primary structural modeling analysis, based on initial never-smokers, used an autoregressive model (entering T2 mediator values adjusted for T1 values) to test for mediational pathways in the relation between e-cigarette use at T1 and cigarette smoking status at T2. Results showed that e-cigarette use was related to all of the mediators. Tests of indirect effects indicated that changes in expectancies, affiliations, and marijuana use were significant pathways in the relation between e-cigarette use and smoking onset. A direct effect from e-cigarette use to smoking onset was nonsignificant. Findings were replicated across autoregressive and prospective models. We conclude that the relation between adolescent e-cigarette use and smoking onset is in part attributable to cognitive and social processes that follow from e-cigarette use. Further research is needed to understand the relative role of nicotine and psychosocial factors in smoking onset.