This paper studied the mediating effect of psychological empowerment on the relationship between transformational leadership and proactive work behavior. Psychological empowerment is hypothesized to provide a comprehensive motivational mechanism clarifying the relationship between transformational leadership and employee work-related behaviors (i.e. proactive work behavior). With an empirical research of 409 Chinese employees, the relationship of transformational leadership on proactive work behavior is positive totally through perceiving of psychological empowerment.