Burnout Syndrome (BS) is a psychological reaction related to chronic occupational stress, both interpersonal and emotional. This study assessed three discriminant profiles of BS in teachers according to psychosocial factors. Profile 1 represents teachers with or without BS; Profile 2 represents teachers with BS or without BS in reference to the dimension guilt; and Profile 3 represents Profile 1 and Profile 2. The sample comprised 679 Brazilian primary school teachers. The instruments used were: sociodemographic data questionnaire; Spanish Burnout Inventory; and Battery of Psychosocial Risk Assessment to assess role ambiguity, social support, self-efficacy, autonomy, role conflict, and overload and intention to leave the profession. Differences between the groups were assessed using discriminant analysis. Results show that the variables that compose the discriminant profiles (Profile 1 and Profile 2) were intention to leave the profession, overload, role conflict, and role ambiguity, with self-efficacy discriminating teachers without BS in Profile 1. Profiles 1 and 2 were discriminated by two determinant factors: role conflict, and intention to leave the profession. The results suggest a need for interventions on psychosocial stressors to prevent burnout.