This study examined the relationship between coping strategies, dispositional optimism, academic burnout and academic performance using structural equation modelling. Data were collected from a sample of 532 Spanish undergraduate students. Participants completed a battery of questionnaires including the LOT-R to assess optimism, CSI for the measurement of coping (adaptive and maladaptive coping strategies), and MBI-SS to evaluate academic burnout (exhaustion, cynicism, and efficacy). Academic performance was evaluated by the grade point average (GPA). The results showed that academic burnout was directly and positively associated with maladaptive coping but directly and negatively explained by adaptive coping. In addition, emotional exhaustion was significantly and negatively predicted by optimism. Finally, academic performance was significantly predicted by academic burnout. In conclusion, the findings suggest that both adaptive coping and optimism help to prevent academic burnout and, therefore, positively affect academic performance. Implications for intervention and future research are discussed.