Using samples of high-tech enterprises, this paper studied the mechanism of impact of transformational leadership (TL) on employees’ innovative behavior (EIB) through dyad questionnaire survey, specifically explored the mediating role of psychological empowerment between TL and EIB and the moderating role of affective commitment in such relationship. The results showed that TL was positively related to EIB; TL was positively related to employees’ psychological empowerment; employees’ psychological empowerment was positively related to their affective commitment to the organization; employees’ affective commitment was a moderator between TL and EIB; and employees’ psychological empowerment including its dimensions acts as partial mediators between TL and EIB.