Amid the concurrent advancement of green transformation and intelligent upgrading, AI digital employees—virtual agents combining technological tool attributes with quasi-social employee characteristics—are increasingly embedded in corporate green technology innovation activities. However, prior research has largely examined the innovation effect of AI from a macro-level digitalization or technology adoption perspective, leaving the underlying mechanisms through which AI digital employees, as a micro-level organizational element, affect corporate green technology innovation insufficiently understood. Drawing on the stimulus–organism–response (SOR) framework, the organizational ambidexterity theory, and the dynamic capability theory, this paper develops a theoretical model explaining how AI digital employees affect corporate green technology innovation. The results show that AI digital employees significantly promote corporate green technology innovation. Organizational ambidexterity and green dynamic capability jointly exert a chain mediating effect in this relationship. Moreover, employee AI literacy and green structured capital positively moderate the proposed mechanisms. This paper reveals the mechanism of AI digital employees on corporate green technology innovation, and provides a reference for intelligent manufacturing firms to realize green transformation by using AI digital employees.