Teachers and peers are two influential social agents in students' academic functioning. In the present study, we differentiated perceived social relationships into positive and negative aspects and investigated how these perceptions influence students' motivation and educational outcomes. Results based on 2211 Chinese middle school students revealed that the perceived teacher relationships emerged as more important predictors than perceived peer relationships. Differential aspects of perceived social relationships also showed distinct predictive patterns. Moreover, multiple-group comparisons further revealed that girls were more sensitive to negative teacher relationships, whereas boys were more sensitive to negative peer relationships. These findings highlight the importance of including multiple aspects of perceived social relationships and considering potential gender differences to more fully capture the factors that affect adolescents' academic functioning.