Social cognitive theory is applied to explore the impact mechanism of transformational leadership on employee’s learning behaviors from failures based on the context of enterprise innovation failures. Data of 461 employees in 12 high-tech enterprises have been obtained via questionnaire survey method, and then empirical analysis is conducted. The results show that there is a significant positive correlation between transformational leadership and employee’s learning behaviors from failures in the context of enterprise innovation failures. Organizational psychological ownership and perceived organizational support have a partial mediating effect on transformational leadership and employee’s learning behaviors from failures. Such mediating mechanism contains three paths: conduction through the organization psychological ownership; conduction through perceived organizational support; and conduction through effect of the perceived organizational support on organization psychological ownership of conduction.