Breakthrough innovations present both opportunities and challenges for firms navigating unpredictable technological and market dynamics, which is significant to firms' sustainable development. However, the impact of strategic alliances on breakthrough innovations remains contested, and the underlying mechanisms are yet to be fully clarified. Drawing on ambidexterity theory and profiting from innovation (PFI) theory, this study investigates the relationships among ambidextrous (exploratory vs. exploitative) alliances, complementary assets, and firms' breakthrough innovations. By analyzing 279 questionnaire responses from Chinese firms, we demonstrate that both exploratory and exploitative alliances, alongside complementary assets, significantly enhance breakthrough innovations. Furthermore, complementary assets play a complete mediating role between exploratory alliances and breakthrough market innovations. In addition, complementary assets also play a partial mediating role between exploratory alliances and breakthrough technological innovations, as well as between exploitative alliances and both breakthrough technological and market innovations. These findings advance ambidextrous theory by delineating the ambidextrous roles of alliances, extend PFI theory through the integration of the mediating roles of complementary assets, and offer actionable insights for managers seeking to leverage ambidextrous alliances for breakthrough innovation success.