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Principal leadership is an important external environmental factor that affects teachers' job burnout. This study investigates whether and how principal’s transformational leadership contributes to teachers’ job burnout. Data collected from 990 teachers in 14 primary school in mainland China were analyzed using regression analysis and bootstrapping tests. The results found that: transformational leadership has a significant negative predictive effect on teachers’ job burnout; Teachers' social emotional competence and student-teacher relationship play an independent intermediary role between the principal's transformational leadership and teacher burnout;Teacher's social emotional competence and student-teacher relationship play a chain mediating role between principal transformational leadership and teacher burnout.