Previous studies have shown that peer relationship affects learning engagement. And learning engagement plays a vital role in promoting knowledge acquisition and production, enhancing adolescents’ academic success. However, few studies have focused on the mechanism between peer relationship and learning engagement. As such, based on Social Cognitive Theory, this study attempts to explore how peer relationship of adolescents is linked to learning engagement through the chain mediating roles of self-efficacy and academic resilience. The participants were 250 students who were selected via random sampling in a public middle school, in Eastern China, in June 2021. All the participants filled in the structured self-report questionnaires on peer relationship, self-efficacy, academic resilience, and learning engagement. The data were analyzed with structural equation modeling (SEM) in SPSS 24.0 and AMOS 24.0. Results indicated that peer relationship was directly and positively associated with learning engagement. Results also indicated that peer relationship was indirectly and positively associated with learning engagement via self-efficacy and academic resilience, respectively, and sequentially. More importantly, it was found that the direct effect was much lower than the indirect effects of which self-efficacy was the greatest. It is suggested that appropriate interventions and support should be provided to facilitate adolescents’ peer relationship, self-efficacy, and academic resilience, thus promoting their learning engagement and academic success.