While individuals’ proactive career behaviors (PCBs) are critical to sustainable career outcomes, knowledge of how and when PCBs translate into these outcomes is limited. Drawing upon the conservation of resources theory and the socially embedded model of thriving, this study examines the psychological process through which PCBs translate into two sustainable career outcomes (i.e., subjective career success and perceived employability). Based on data collected from 228 participants in a Chinese company, our findings reveal that PCBs positively predict subjective career success and perceived employability by fostering thriving at work. Furthermore, the indirect association between PCBs and perceived employability via thriving at work is strengthened when participants’ perception of humble leadership is high. This study extends our knowledge by identifying a psychological mechanism that explains how employees’ PCBs translate into sustainable career outcomes and enriches our understanding of the boundary conditions of PCBs by identifying humble leadership as an important factor.