As a micro unit of the major producer of environmental pollution, enterprises investment in environmental protection is an important way of environmental protection. As a self financing economic entity, has the enterprises environmental investment damaged the value of the enterprise? Based on the sample of listed companies from 2008 to 2018, the empirical research shows that: the U shaped relationship between corporate environmental investment and corporate value first decreases and then increases; CEO’s overseas experience significantly moderates the nonlinear relationship between corporate environmental investment and corporate value. In addition, further research finds that under the high level of financing constraints, the CEO’s overseas experience plays a more significant role in enhancing the corporate value and regulating the environmental investment and corporate value. The research results expand the analysis of the impact of environmental investment on corporate value, and provide a new perspective for the existing human capital management of selecting overseas experienced executives.