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Academic burnout, characterized by emotional exhaustion, depersonalization, and diminished personal accomplishment, represents a critical issue among Chinese undergraduates. This study surveyed 308 students to examine how academic stress and social comparative self-assessment contribute to burnout, focusing on gender differences. A newly developed two-dimensional self-assessment scale measured perceived competence in learning behaviors and abilities. Results showed that female students reported higher emotional exhaustion and lower accomplishment than males. Academic stress fully mediated the gender–burnout link, while self-assessments partially mediated the effect of stress on burnout. Gender also moderated the stress–ability self-assessment relationship, with females more vulnerable. Findings underscore the interplay between external stressors and internal comparisons, highlighting the need for targeted interventions, especially for female students.