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As market competition continuously intensifies, how to cope with existing and potential market challenges in complex, dynamic environments is a major problem haunting Chinese e-commerce enterprises in their strategic planning. In order to solve this problem, the theory of organizational ambidexterity is applied in this paper to the strategic practices of Chinese e-commerce enterprises, and starting from the view of corporate leadership, the mediated role of top management’s behavioral integration (referred to as TMBI in the following content) in the relationship between transformational leadership behavior and organizational ambidexterity is discussed. In addition, against the practical background that Chinese e-commerce enterprises are facing highly competitive environments, further clarification is made herein by using environmental dynamics as the moderator variable for the mediated link. Through empirical tests on 198 samples of Chinese e-commerce enterprises, we find that: 1) transformational leadership has a positive influence on organizational ambidexterity, and TMBI plays a full mediated role in that influencing process; 2) environmental dynamics moderates the relationship between transformational leadership and TMBI, but don’t have a moderated effect on the relationship between TMBI and organizational ambidexterity. According to the research conclusion in this paper, the mechanism of transformational leadership influencing organizational ambidexterity can be better explained when two important factors, TMBI and environmental dynamics, are taken into consideration. The research in this paper provides not only important revelations for the development of organizational ambidexterity research as well as the application of relevant research achievements, but also supports for Chinese e-commerce enterprises’ effective strategic practices in theory.