How to enhance innovation performance through effective entrepreneurial learning mechanisms has become a significant challenge for new ventures, yet existing research has paid limited attention to this issue. Based on organizational learning theory (OLT) and resource-based theory (RBT), this study explores the impact of ambidextrous entrepreneurial learning on new venture innovation performance from the perspective of ambidextrous learning. Additionally, it examines the roles of serendipity and environmental munificence in this process. Using multiple linear regression and Bootstrap methods, the study analyses survey data from 301 enterprises. The results indicate that ambidextrous entrepreneurial learning positively influences the new venture innovation performance. Serendipity mediates the relationship between ambidextrous entrepreneurial learning and innovation performance, while environmental munificence positively moderates this relationship. The findings extend the antecedents of new venture innovation performance, contribute to the development of serendipity theory in the domestic context, and provide important insights and references for new ventures seeking to improve their innovation performance.