Using the revised job demands-resources model, this study aimed to analyze the direct relationship of teacher self-efficacy with burnout and its indirect relationship through perceived social support as well as the moderating roles of teacher optimism in these relationships. The study used a Bayesian estimator with structural equation modeling to examine the structural relationships among self-efficacy, optimism, perceived social support, and burnout, using data collected from a sample of 288 teachers in Elâzig, a city in the eastern region of Turkey. The results demonstrated the negative relationships between teacher self-efficacy and optimism with burnout, and the indirect negative relationship between teacher self-efficacy and burnout through perceived social support. In addition, the present study revealed that the direct relationship between teacher self-efficacy and perceived social support and the indirect relationship between teacher self-efficacy and burnout through perceived social support can be strengthened depending on the level of optimism. Recommendations for practitioners, policymakers, and researchers are presented.