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We examined how high school students’ (N = 636) perceptions of classroom goal structures were longitudinally related to their motivation and learning outcomes in health education. Guided by expectancy-value theory, we incorporated two aspects of motivation: students’ self-efficacy for negotiating condom use and task values for learning new information about HIV and pregnancy prevention. Results from cross-lagged models demonstrated that perceived mastery goal structure positively predicted longitudinal changes in students’ self-efficacy and task values. Self-efficacy and task values, in turn, positively predicted achievement and behavioral intentions to use a condom, even after controlling for prior achievement and intentions. Findings suggest that self-efficacy and task values serve as a motivational pathway that links perceived mastery goal structure to educational outcomes.