Although temperament and motivation both reflect individual differences in what is perceived as rewarding or threatening, and what is to be approached and what avoided, respectively, we know rather little about how they are connected in educational settings. In this study, we examined how different aspects of temperament (reward and punishment sensitivities) predict the goals students seek to achieve in relation to learning and performance. In Study 1, four dimensions describing students' temperament (sensitivity to punishment, intra-individual reward sensitivity, inter-individual reward sensitivity, and positive expressiveness) were uncovered, and in Study 2, these were used to predict students' achievement goal orientations (mastery-intrinsic, mastery-extrinsic, performance-approach, performance-avoidance, and avoidance). The results of exploratory structural equation modeling revealed significant predictions on all achievement goal orientations. In line with theoretical assumptions, sensitivity to punishment was predictive of performance orientations, intra-individual reward sensitivity of mastery orientations, and inter-individual reward sensitivity of performance and avoidance orientations. Positive expressiveness only had weak negative effects on performance orientations. The findings suggest that the goals and outcomes students seek to attain in an educational context are partly dictated by their sensitivity to different environmental cues and the kinds of affective and behavioural responses these typically incite.