This study explored the relationships among teachers’ emotional competence, burnout as a mediator, and social support. Teachers’ emotional competence was assessed via measures of emotional intensity and emotional regulation. Social support was evaluated in terms of external versus internal support, and teacher dissatisfaction with support received. Participants were 149 Italian primary school teachers. Data were analysed using structural equation modelling. The findings suggested that teacher burnout partially mediated the relationship between emotional intensity and satisfaction with social support received. Overall, the results showed that teachers were at risk of highly intense unpleasant emotions in relation to their burnout syndrome. Moreover, teachers’ satisfaction/dissatisfaction with social support received was predicted by burnout symptoms. These results extend the findings of earlier studies, and provide indications as to how to help teachers experiencing burnout.