The aim of this study was to analyze the relationship between Big-Five personality traits, perceived self-efficacy (GSES) and dimensions of occupational burnout in accordance with Christina Maslach’s three-factor burnout model (emotional burnout, depersonalization, perceived lack of own accomplishments). Data collected among 271 teachers (82% female) aged 20–68 confirmed findings from previous research that four personality traits (Neuroticism, Extraversion, Agreeableness, Conscientiousness) are correlated with burnout and that they are significant predictors for all dimensions of burnout. In addition, it was shown that GSES plays a moderating role as a buffer that protects people with high levels of neuroticism from a sense of lack of own accomplishments. It was also found that GSES plays a mediating role for the relationship between Extraversion, Conscientiousness and Neuroticism and perceived lack of own accomplishments and that it is a suppressor for the relationship of neuroticism with emotional exhaustion. The results are discussed in the context of personality theories and their possible applications.