This article discussed the structural relationship among socio-cognitive and affective variables on secondary teachers’ job satisfaction, focusing on multiple paths from teacher efficacy to teachers’ job satisfaction via social-emotional competence and burnout in middle school contexts. Using panel data of 853 middle school teachers, the latent moderated structural equation approach was applied to test multiple mediations and moderated mediation effect by Mplus 8.4. According to research findings, despite teachers’ burnout showing a negative effect on the teachers’ job satisfaction, teacher efficacy and social-emotional competence positively affected the teachers’ job satisfaction. Besides, a positive simple mediation effect of teacher efficacy on teachers’ job satisfaction via social-emotional competence and a positive serial multiple mediation effect of teacher efficacy on teachers’ job satisfaction via social-emotional competence and burnout in order was found. Lastly, in the moderated mediation effect test, no mediation effect of teacher efficacy on teachers’ job satisfaction via burnout and no moderated mediation effect of social-emotional competence on the mediation effect was found, respectively. However, a negative moderation effect of social-emotional competence between teacher efficacy and teachers’ job satisfaction was identified. Based on the results of this study, in-depth suggestions were made on expanding our theoretical knowledge of socio-cognitive and affective factors and their applications for teachers’ job satisfaction.