Background: Although previous studies indicate that chronotype might be associated with risk-taking behavior, the specific mechanism has not been thoroughly discussed. This study aimed to fill this gap by exploring the mediating role of self-control and the chain mediating role of self-control and emotional stability between chronotype and risk-taking behavior. Methods: A total of 547 Chinese college students between 18 and 24 years old were selected to complete the Morningness–Eveningness Questionnaire (MEQ), Self-Control Scale (SCS), Eysenck’s Personality Questionnaire-neuroticism (EPQ-N), and Adolescent Risk-Taking Questionnaire: Risk Behavior Scale (ARQ-RB) to assess chronotype, risk-taking behavior, self-control, and emotional stability, respectively. Hayes’ PROCESS macro for SPSS was used to test the relationships among these variables. Results: Our result showed significant positive correlations among chronotype, self-control, emotional stability, and significant negative correlations between self-control, emotional stability, and risk-taking behavior. We also found that chronotype had a significant predictive effect on risk-taking behavior in the chain mediation model. Specifically, chronotype affected risk-taking behavior through two pathways: the separate mediating role of self-control and the serial mediation pathway of self-control → emotional stability. Conclusions: Our study provides direct evidence that chronotype is associated with risk-taking behavior. The results showed that the predictive function of chronotype was mediated by self-control and emotional stability. This study provides a new perspective on preventing and reducing risk-taking behavior.