Chinese enterprises’ outward foreign direct investment（OFDI）not only considers the business environment of the target country，but also the economic benefits of the investment. How to ensure the safety of investment projects in the process of participating in foreign direct investment and integrate the benefits brought by the global value chain is an important part of promoting the “Belt and Road” construction. This article considers the 2013 “Belt and Road” initiative policy as a quasi-natural experiment，using the difference-in-difference method to analyze the promotion effect of the “Belt and Road” initiative policy on Chinese enterprises’ direct foreign investment and its effect in countries（regions）along the “Belt and Road”，we also use the business environment score indicators obtained by factor analysis to further analyze the impact of the business environment of the countries（regions）along the “Belt and Road” on China’s acceptance of OFDI. The research results show that the introduction of the “Belt and Road” initiative policy has significantly promoted Chinese companies foreign direct investment in countries along the “Belt and Road”，and the promotion effect is not sustainable. The better the business environment is，the better it is to attract China’s OFDI. It provides empirical evidence for evaluating the effects of the “Belt and Road” policy. It is suggested that efforts to improve the business environment through the efforts of two or more parties can provide a reference for the precise implementation of the “Belt and Road” initiative to promote the participation of Chinese enterprises in the division of global value chains and expand opening up.