Since the first half of the 1980s, burnout in teachers has been the object of particular attention by many international authors. Teachers are subject, more than other professions, to numerous and heavy pressures, covering the peculiarity of the profession. The objectives of the present research are to measure the predictive role of emotional exhaustion, depersonalization, and personal accomplishment on the quality of teaching in a group of elementary school teachers. We carried out a cross-sectional study involving 324 Sicilian female teachers, who worked in three school orders: Kindergarten, primary school, and the first year of middle school. Participants completed a socio-demographic questionnaire, the assessment teaching scale for primary school teachers (ECAD-EP), and the Maslach Burnout Inventory (MBI). In reference to the level of burnout, the correlation analysis underlined the presence of a positive correlation between: Emotional exhaustion and depersonalization; and a negative correlation between exhaustion and depersonalization. Furthermore, a predictive role of emotional exhaustion, depersonalization, and personal accomplishment on the quality of teaching in a group of primary school teachers was found.