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We investigated the role of classroom goal structures in adolescent students’ future choice intentions and achievement, focusing on the potential mediating roles of expectancy-value beliefs. Results from 634 Chinese adolescent students revealed that different expectancy-value beliefs demonstrated distinct mediating pathways, consistent across math and English domains. Specifically, self-efficacy positively mediated the relationships between classroom mastery goal structure and future choice intentions and achievement. Interest value positively mediated the relationship between mastery goal structure and future choice intentions yet negatively mediated the relationship between performance-approach goal structure and future choice intentions. Moreover, effort cost negatively mediated the relationship between performance-avoid goal structure and achievement. Findings highlight the importance of recognizing contextual factors and multiple expectancy-value beliefs when predicting students’ academic outcomes.