Proper pressure can stimulate principals of rural primary schools’ potential. But if principals of rural primary schools can’t cope with pressure successfully, and the pressure has not been released for a long period of time, he/she will be anxious, depressed, tired out and will descend in working efficiency, even be exhausted. The phenomenon is called job burnout. It is not only directly influence the physical and mental health of principals of rural primary schools, but also serious influence their interpersonal relationships and work capability. So it is completely necessary to investigate the potential mechanisms of principals of rural primary schools’ job burnout so as to design effective prevention and intervention programs. Among many factors affecting principals of rural primary schools’ job burnout, the role of emotional intelligence has increasingly been recognized by both practitioners and researchers over the past few years. There is literature documenting that emotional intelligence has an important influence on principals of rural primary schools’ job burnout, but little is known about mediating processes underlying this relation. In relative literatures, leadership efficiency and job satisfaction are conducive to the decline of principals of rural primary schools’ job burnout. Leadership efficiency and job satisfaction are the reliable and powerful predictors of principals of rural primary schools’ job burnout. So we tested whether leadership efficiency and job satisfaction served as mediators of the relationship between emotional intelligence and principals of rural primary schools’ job burnout. To examine how emotional intelligence influenced principals of rural primary schools’ job burnout, 258 principals of rural primary schools were recruited in the study to complete self-report questionnaires. Emotional intelligence was measured with the emotional intelligence scale which consists of 16 items. The respondents rated the extent to which they agreed with each statement on a 7-point Likert scale. Leadership efficiency was measured with the leadership efficiency scale which consists of 9 items. The respondents rated the extent to which they agreed with each statement on a 5-point Likert scale. Job satisfaction was measured with the job satisfaction questionnaire which consists of 8 items. The respondents rated the extent to which they agreed with each statement on a 7-point Likert scale. Job burnout was measured with the job burnout questionnaire which consists of 22 items. The respondents rated the extent to which they agreed with each statement on a 5-point Likert scale. The results implicated that: ① Emotional intelligence significantly negatively predicted principals of rural primary schools’ job burnout; ② Leadership efficiency mediated the effect of emotional intelligence on principals of rural primary schools’ job burnout; ③ Job satisfaction mediated the effect of leadership efficiency on principals of rural primary schools’ job burnout. Therefore, leadership efficiency and job satisfaction played chain mediating effect between emotional intelligence and principals of rural primary schools’ job burnout. These findings supported our model that the link between emotional intelligence and principals of rural primary schools’ job burnout was complex. The conclusion of the study had important reference value for preventing and reducing principals of rural primary schools’ job burnout.