Introduction and Aims A growing body of evidence suggests e-cigarette use increases the risk of conventional cigarette use. Assessing the factors associated with intentions to use e-cigarettes can inform programs designed to minimise uptake, potentially assisting in preventing a new population of smokers. This study developed and tested a model assessing the importance of various factors that may be associated with intentions to use e-cigarettes among young adults who have never used e-cigarettes or tobacco cigarettes. Design and Methods A web-panel provider recruited 429 Australian 18- to 25-year-olds who had never used e-cigarettes or smoked tobacco cigarettes (56% female, mean age = 21.17 years). Various individual and social factors were assessed as potential direct and indirect predictors of e-cigarette use intentions. Results The developed model provided an excellent fit to the data and accounted for 49% of the variance in use intentions. Males had greater intentions to use e-cigarettes compared to females (beta = -0.13). Having a greater number of friends who smoke tobacco cigarettes (beta = 0.11) and curiosity about e-cigarette use (beta = 0.58) were also directly associated with greater use intentions. Positive expectancies about e-cigarettes (beta = 0.14), having family members who use e-cigarettes (beta = 0.11), and having friends who smoke tobacco cigarettes (beta = 0.07) were indirectly associated with intentions via curiosity. Discussion and Conclusions Curiosity about e-cigarette use was strongly associated with use intentions. Aspects of the social environment were also important. Further research is needed to identify effective means of challenging positive e-cigarette expectancies given these were found to be strongly associated with intentions via curiosity.