A chief executive officer (CEO) acting as the firm's transformational leader is typically viewed as instrumental to corporate entrepreneurship in established firms, but how exactly does a higher level of corporate entrepreneurship come about, given a transformational CEO's actions? We suggest that organizational ambidexterity can function as a core mediating mechanism between transformational CEOs and the observed level of corporate entrepreneurship and that the effectiveness of this mediating process varies as a function of critical contingencies related to characteristics of the top management team (TMT), the environment and the organization's design. Our empirical evidence, based on a sample of 145 Chinese private sector firms, and using three primary sources of data (145 CEOs, 506 TMT members, and 1,981 middle managers), provides support for a moderated mediation process. We find that the mediating pathway from transformational leadership to corporate entrepreneurship through organizational ambidexterity is not significant when boundary conditions are ignored. However, when environmental dynamism, TMT collectivism, and structural differentiation are included as moderators, CEO transformational leadership does affect corporate entrepreneurship via the creation and effective functioning of organizational ambidexterity.