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Drawing upon situated expectancy-value theory, we examined whether relatedness satisfaction and frustration have different predictive relationships with adolescents’ academic motivation and educational outcomes in math. Results based on 838 Chinese adolescent students revealed that relatedness satisfaction positively predicted self-efficacy, which in turn led to higher achievement. It also positively predicted interest value, leading to higher positive classroom affect and lower negative classroom affect. In contrast, relatedness frustration negatively predicted self-efficacy and directly predicted classroom affect. It also negatively predicted interest value and positively predicted effort cost, which led to lower positive classroom affect and higher negative classroom affect. These findings highlight the importance of differentiating between relatedness satisfaction and frustration when predicting students’ academic motivation and educational outcomes.