Based on the interaction of person-affect-cognition-execution model, this study examined the association between stress perception and problematic social network use among Chinese college students and explored the mediating effect of the fear of missing out (FoMO) on the relationship between stress perception and problematic social network use. A questionnaire survey was conducted among 554 students from nine universities in China. We found that stress perception was significantly positively correlated with problematic social network use and FoMO (r = 0.38, 0.46;p< 0.001), and FoMO was significantly positively correlated with problematic social network use (r = 0.45,p< 0.001). FoMO mediated the relationship between stress perception and problematic social network use. Conclusion: Stress perception has a negative impact on college students’ problematic social network use via the mediating effect of FoMO. Practical implications that reveal the college students’ problematic social network use were discussed as well.