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We studied the formation of leaders’ habitual behaviors and the impact of leaders’ existing and potential capabilities on ambidextrous (i.e., exploitative and exploratory) innovation activities. Leadership habitual domain (LHD) theory was applied from an endogenous perspective to analyze the impact mechanism of LHD on ambidextrous innovation via the mediating role of dynamic capabilities. We used structural equation modeling to test data collected from 205 team leaders in East China. Results showed that LHD was positively associated with both exploitative and exploratory innovation, and that dynamic capabilities mediated these relationships. Thus, team leaders should renew, reconfigure, and expand their LHD by sensing and seizing opportunities when implementing ambidextrous innovation.