This study aimed to investigate the relationship between effort-reward imbalance and learning engagement and the chain mediating role of academic self-concept and burnout in this relationship. A total of 1030 adolescent students were assessed via the Effort-Reward Imbalance for Learning Scale, the General Academic Self Scale for Adolescents, the Adolescent Learning Burnout Scale, and the Utrecht Work Engagement Scale-Student. (1) Effort-reward imbalance, learning engagement, academic self-concept, and academic burnout were significantly correlated. (2) Although the direct effect of effort-reward imbalance on learning engagement was not significant, the chain mediating role of academic self-concept and academic burnout in the relationship between effort-reward imbalance and learning engagement was significant. Effort-reward imbalance predicts learning engagement via the chain mediating role of academic self-concept and burnout. Teachers and parents should pay attention to the potential impact of students' negative academic self-concept and burnout induced by the effort-reward imbalance on learning engagement.