How to improve the performance of enterprise technology innovation is a problem that innovative enterprises must face in the era of knowledge economy. Previous studies have explored the impact of knowledge transfer on the technological innovation performance on the objective level, but there has been inadequate concern for the influence mechanism on the subjective level. Through the investigation of 232 staff in high-tech enterprises, this study explores the effect of knowledge transfer mechanism on the technological innovation performance of enterprises from the perspective of psychological capital. The results show that knowledge transfer has a positive predictive effect on the technological innovation performance of high-tech enterprises, and the level of employee psychological capital has a significant mediating effect on knowledge transfer.