Most research on institutional pressure focuses on mature enterprises. However, compared with mature enterprises, new ventures are more sensitive to institutional pressure due to their lack of legitimacy. Based on the theoretical path of “environment–strategy–performance”, this study investigated the influence of institutional pressure on entrepreneurial performance as well as the mediating role of green entrepreneurial orientation and the moderating role of network centrality. An empirical analysis based on 288 survey samples from China showed the following: coercive pressure has not only a direct positive impact but also an indirect positive impact on entrepreneurial performance through green entrepreneurial orientation; normative pressure and mimetic pressure positively affect entrepreneurial performance through green entrepreneurial orientation; green entrepreneurial orientation has a positive impact on entrepreneurial performance; network centrality positively regulates the relationships between coercive pressure, mimetic pressure, normative pressure and green entrepreneurial orientation. The paper concluded by highlighting the importance of the conclusions for new ventures to improve their performance as well as for policy makers to optimize the institutional environment for entrepreneurship.