Drawn from social network theory and ambidextrous learning view, a moderated mediation model was constructed to explore the impact of network orientation on new venture performance, and to further examine the mediating effect of ambidextrous learning and the moderating role of environmental dynamism. Based on the data from 285 Chinese start-ups, the empirical study was conducted by using the bootstrapping method. The results demonstrate that network orientation has a significant positive impact on new venture performance. Network orientation positively affects exploratory learning and exploitative learning. Exploratory learning and exploitative learning fully mediate the relationship between network orientation and new venture performance. Environmental dynamism negatively moderates the mediated path through exploitative learning, however, has no moderating effect on the mediated path through exploratory learning.