The aim of this study was to examine the relationship between Perceived Emotional Intelligence (PEI) and Affect balance (positive and negative) along with their impact in the prediction of the burnout syndrome in a Spanish sample of primary school teachers. Furthermore, a model of relations using structural equation modeling (SEM) analyzing the predictive role of both PEI components and Affect on burnout dimensions is proposed. A sample of 251 teachers completed a set of questionnaires that included the variables of interest. Results show that the model proposed accounts for 37% of the variance in emotional exhaustion, 57% of the variance in depersonalization and 67% of the variance of personal accomplishment. Putting all variables together, the model explained 80% of the latent burnout variable. The implications and limitations of the study are explained.