This study examined the relationship among teachers’ psychological and structural empowerment, positive psychological capital, and teachers’ burnout(emotional exhaustion, depersonalization, personal accomplishment-reverse) and how positive psychological capital moderated this relationship. A total of 334 teachers working in elementary, middle and high schools in the survey and a structural equation model was utilized to conduct data analysis. Data analysis was conducted using SPSS 24.0 and AMOS 24.0 to verify the validity of the measurement model, the fit of the structural regression model and the direct and indirect effects of variance. The results of the study were as follows. First, a teacher s psychological empowerment had a negative effect on personal accomplishment-reverse and a teacher s structural empowerment had a negative effect on emotional exhaustion. Second, Psychological empowerment had a statistically significant effect on positive psychological capital. Structural empowerment had no significant effect on positive psychological capital. Third, positive psychological capital had a negative effect for all sub-factories of teachers’ exhaustion. Fourth, positive psychological capital has full mediated effects on the relationships between psychological empowerment and emotional exhaustion, psychological empowerment and depersonalization. The mediators have only partial mediated effects on the relationship between psychological empowerment and personal accomplishment-reverse. From these results, the meaning of this study and implications for subsequent studies were discussed.