Background: Dual use of e-cigarettes and combustible tobacco products is common in young adults. We aimed to explore how ratings of subjective and contextual factors differed between discrete episodes of e-cigarette use vs. combustible tobacco product smoking among a sample of young adults. Methods: Young adults (N = 29, ages 18–30) who used e-cigarettes and ≥1 combustible tobacco product at least once weekly completed a 1-week smartphone-based ecological momentary assessment (EMA). Twice daily random prompts assessed past-15-min use of tobacco products, ratings of subjective factors (e.g., negative affect, craving), and contextual factors related to activity, location, and companionship. A multivariable GEE model assessed whether subjective or contextual factors were associated with e-cigarette vs. combustible tobacco product episodes. Results: 184 tobacco use episodes were reported (39.7% e-cigarette, 60.3% combustible tobacco product). High baseline cigarette dependence, as measured by the Fagerström Test for Cigarette Dependence, was associated with lower odds of e-cigarette vs. combustible tobacco product episodes (aOR 0.01, 95% CI (0.002–0.08); p < 0.001). Neither between- or within-subjects negative affect or craving scores were associated with e-cigarette use. Activities of eating/drinking (aOR 0.20, 95% CI (0.08–0.49); p = 0.001) and being in the companionship of a person who smoked cigarettes (aOR 0.13, 95% CI (0.04–0.43); p = 0.001) were associated with lower odds of e-cigarette vs. combustible tobacco product use episodes. However, traveling (aOR 12.02, 95% CI (3.77–38.26); p ≤ 0.001) and being in a public space (aOR 2.76, 95% CI (1.10–6.96); p = 0.03) were associated with higher odds of e-cigarette than combustible tobacco product use episodes. Conclusions: This pilot data suggests that unique contextual factors may be associated with e-cigarette use, compared to combustible tobacco smoking in a sample of young adults who use both e-cigarettes and combustible tobacco products. Future research with larger samples is needed to better characterize varying contexts and cues for tobacco use among young adults who are dual users.