IntroductionDemographic and health factors are known to predict vaping. Less is known about psychological predictors of vaping uptake, particularly among non‐smoking adults using longitudinal designs. We aimed to model how psychological factors related to personality and mental health predicted the likelihood of vaping uptake over time in non‐smoking adults ages 18+ using longitudinal data.MethodsLongitudinal regression models utilised data from the 2018–2020 waves of the New Zealand Attitudes and Values Study to assess how the Big Five personality traits, mental distress and self‐control predicted who began vaping over time among non‐users (non‐vapers and non‐smokers), controlling for gender, age, ethnicity and economic deprivation.ResultsAnalyses included 36,309 adults overall (ages 18 to 99; M = 51.0). The number of non‐users who transitioned into current vaping was small (transitioned from 2018 to 2019, n = 147; 0.48%; 2019 to 2020, n = 189, 0.63%). Fully adjusted models showed that adults with higher mental distress (adjusted odds ratio [aOR] 1.43; 95% confidence interval [CI] 1.09–1.88), lower self‐control (aOR 0.79; 95% CI 0.69–0.89) and higher extraversion (aOR 1.09; 95% CI 1.06–1.13) were more likely to begin vaping at the next time point compared to adults who remained non‐users. Higher neuroticism and lower conscientiousness also predicted vaping uptake in initial models, but inclusion of mental distress and self‐control superseded these traits.Discussion and ConclusionsPsychological factors related to mental distress, impulse control and sociability predicted who was more likely to begin vaping as non‐smoking adults. Harm prevention interventions could target these factors to reduce vaping uptake in non‐smokers.