This study examined direct associations between emotional competence, perceived stress and burnout in 489 Spanish teachers. In addition, a model in which perceived stress mediated pathways linking emotional competence to teacher burnout symptoms was also examined. Results showed that emotional competence and stress were significantly correlated with teacher burnout symptoms in the expected direction. Moreover, mediational analysis indicated that perceived stress partly mediated the relationship between emotional competence and the three dimensions of burnout even when controlling for salient background characteristics. These findings suggest an underlying process by which high emotional competence may increase the capacity to cope with symptoms of burnout, by reducing the experience of stress. Implications of these findings for future research and for working with teachers to prevent burnout are discussed.