Factors related to grade point average (GPA) are of great importance for students' success. Yet, little is known about the impact of individual differences in emotional reactivity on students' academic performance. We aimed to examine the emotional reactivity-GPA link and to assess whether self-esteem and psychological distress moderate this relationship. Eighty undergraduate students reported on their GPA, self-esteem, and psychological distress. Students' pupil radius was monitored during affective picture viewing to assess sympathetic activation in response to emotional stimuli. Cluster analysis on pupil reactivity to pictures identified low, average, and high emotionally reactive students. Regression analyses indicated that profiles of emotional reactivity were associated with GPA. This relationship was moderated by self-esteem, but not psychological distress. Among students with higher emotional reactivity, those with lower self-esteem reported poorer GPA. Findings document the importance of differences in students' emotional reactivity and self-esteem in relation to academic success.