The concept of approaching psychological capital (PsyCap) as an influencer on behaviors and results at both an individual and an organizational level is gaining support from a growing body of research. However, to date, the construct and impact of the PsyCap on adolescents’ behavioral outcomes have not been tested. If tested, an understanding of the psychological construct and its impact could be helpful for teachers and administrators in adjusting institutional methodology in accordance with the mental health status of the students. We explore the impact of PsyCap and the moderating role of perceived social support. We also adopt an innovative perspective to detect how to reduce problem behaviors. A construct of PsyCap of adolescents and the relationships among PsyCap, perceived social support, and behavioral problems is proposed. The findings provide a strong evidence-based recommendation for the use of PsyCap in a public school education management.