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Despite the salience of achievement emotions in educational theory and research, critical assumptions regarding the antecedents of emotion remain untested. The current study combines perspectives of achievement goal theory (Elliot et al., 2011) and control-value theory (CVT; Pekrun, 2006), to test CVT’s assumption that cognitive appraisals of control and value mediate the effects of achievement goals on emotions. Structural models based on a large sample of introductory psychology students (N = 3628) provide support for CVT. Together, control and value appraisals were strong predictors of a range of discrete emotions (enjoyment, boredom, hope, pride, shame, helplessness), and mediated relationships between goals and emotions. We found strong evidence indicating that mastery goals promote positive emotions indirectly through appraisals of intrinsic value.