Academic performance (i.e., grade point average) determines career entry factors as well as career success and is thus crucial for students' future careers. Besides individual factors such as personality traits, individuals' social embeddedness has been shown to enhance performance. Regarding academic performance, relationships to fellow students (peers), which bundle into one's developmental network, are a valuable source of psychosocial and career support because occupying central positions within a social network provides the benefit of being able to access career-enhancing resources. Integrating individual and social-contextual factors for the purpose of examining academic performance is therefore plausible. Research results indicate that personality, especially extraversion, might predict performance through network centrality. In this study, we examined this assumption by focusing on extraversion and centrality in the peer developmental network of recently acquainted German psychology bachelor students (N = 47, 15% male). In a longitudinal design, we analyzed the impact of extraversion and centrality on students' academic performance at the end of their studies. Results revealed that centrality (i.e., popularity) mediates the relationship of extraversion with academic performance, indicating that extraverted students (regardless of their agreeableness) are more popular among their peers, which, in turn, enhances their academic performance. That is, the likelihood of getting superior final grades depends on whether students manage to attract peers at the very beginning of their university life, which is easier for extraverts. These findings emphasize the importance of the social embeddedness of people, highlight its long-term effects on performance, and yield several implications for research and practice.