Increasingly prominent environmental problems have led to the construction of green competitiveness of manufacturing enterprises becoming an important issue. However, little literature has focused on the construction path of green competitiveness at the enterprise level, and the influence mechanism of green knowledge value on the green competitiveness of manufacturing enterprises needs to be further clarified. Therefore, this study establishes a green knowledge value chain from the perspective of ambidextrous learning based on organizational learning theory and value co-creation theory. Meanwhile, from the resource-based view, this study elucidates the influence mechanism of ambidextrous learning on the green competitiveness of manufacturing enterprises and constructs a moderated mediation model. Through data analysis of 209 manufacturing enterprises, this study has obtained some conclusions as follows. Ambidextrous learning is more effective in enhancing the green competitiveness of manufacturing enterprises. Green value co-creation (GVC) mediates the relationship between ambidextrous learning and the green competitiveness of manufacturing enterprises. Green strategic orientation reinforces the mediating role of GVC. The conclusions of this study contribute to the construction of green competitiveness of manufacturing enterprises by providing an effective way and recommendations for the establishment of GVC and green strategic orientation of manufacturing enterprises.