The mentoring system is regarded as an important tool of enterprise human resource development. It plays a central role in promoting the growth and development of employees and gaining competitive advantages for enterprises. Based on resource conservation theory, this paper explores the influential mechanism between mentoring system and protégés innovation performance. Through the empirical analysis of 318 valid matching sample data, we found: the mentoring system has a positive correlation with protégés' innovation performance; psychological availability plays a partial mediating role between the mentoring system and the protégés' innovative performance; proactive personality not only positively moderates the relationship between mentoring and apprentice psychological availability, but also further moderates the indirect effect of mentoring on apprentice innovation performance through apprentice psychological availability.