This study investigates the impact mechanism of person-organization and person-job fit on their emotional well-being, using a sample of 1128 primary, middle, and high school physical education teachers in China. Additionally, it verifies the chain mediation effects of compassion satisfaction, job burnout, and secondary traumatic stress within this impact mechanism. The results indicate that the person-organization fit and person-job fit significantly affects compassion satisfaction. In turn, compassion satisfaction impacts emotional well-being, secondary traumatic stress, and job burnout. Both job burnout and secondary traumatic stress significantly influence emotional well-being. Compassion satisfaction alone mediates these effects, and together with job burnout and secondary traumatic stress, it forms a chain mediation effect. Finally, this study provides substantive suggestions for the society to pay attention to the emotional well-being of physical education teachers and strive to create a fairer and more valuable work environment.