Burnout is a serious problem in the profession of teaching. Previous studies have found that teachers with high perceived abilities to appraise emotions tend to experience symptoms of burnout less frequently than others. The aim of this study was to investigate processes that may underlie this relation. We hypothesized that teachers' perceived abilities to appraise their own and others' emotions would facilitate proactive coping and attending to student needs. In turn, these antecedent-focused regulation strategies were expected to help teachers deal with emotionally demanding situations at work. We tested the hypotheses using multiple mediation analyses of self-report data from 300 teachers, controlling for general perceived self-efficacy, teaching experience, work demands, and school-level effects. Results showed that both proactive coping and attending to student needs constituted mediators of the relations between self-emotion appraisal and burnout as well as between other-emotion appraisal and burnout. Although we cannot infer causality from the present data, the perceived abilities to appraise their own emotions and those of others may help to protect teachers from burnout by enabling them to prevent potential stressors and to engage with their students effectively.