It is widely acknowledged that non-compliance with smartphone security behaviors is widespread and may cause severe harm to people and devices. In addition to device-based security issues, there are psychological factors involved in these behaviors such as self-efficacy, risk awareness, and social support. The present study examines associations of these three factors with smartphone security behaviors and explores possible mechanisms among these variables. In a longitudinal survey with 192 Chinese college students (73.4% women, mean age 24.46 years, SD = 5.15), self-efficacy, risk awareness, and social support were assessed with psychometric scales at two points in time, 2 weeks apart. Hierarchical regression analyses were performed with follow-up smartphone security behaviors as the dependent variable, controlling for baseline values and demographic and IT-related covariates. Main effects of self-efficacy, risk awareness, and social support on smartphone security behaviors were identified. Moreover, a triple interaction among the three predictors emerged in a synergistic way, indicating that their combination yielded more favorable levels of secure smartphone use. The total model accounted for 50% of the behavioral variance, with all covariates included, and the triple interaction among self-efficacy, risk awareness, and social support accounted for 2.3% of variance. Results document that psychological factors are involved in smartphone security behaviors beyond demographic and IT-related covariates. Interventions could be designed to improve smartphone security behaviors not only by developing privacy-enhancing technologies but also by considering psychological factors such as self-efficacy, risk awareness, and social support.