This study aimed to investigate whether and how university students with high psychological capital (PsyCap) experience more career growth. Based on self-determination theory, we examined the mediating role of self-concordance in choosing majors and the moderating role of career values in this relationship. Results from a two-wave lagged study of 705 Chinese university students over one year provided support for our model. We found that students' PsyCap upon university entrance was positively related to their career growth one year later through the mediating role of self-concordance in choosing majors; extrinsic career values (external compensation and work-life balance values) mitigated the positive effect of self-concordance in choosing majors on career growth, as well as the indirect effect. We contribute by identifying PsyCap as an antecedent of career growth of university students and by revealing its influence mechanisms in a career choice scenario. Practical implications of the study are also discussed.