Under the constraint of enterprise heterogeneity, environmental regulation will affect the re-allocation of resources among products. Appropriate product switching can make China’s export trade powerful, promote the high-quality development of export trade, and realize the win-win situation between environmental protection and export trade. Based on the related theories of environmental economics and international trade, this paper uses the matching data of China’s industrial enterprises and customs import and export trade in 2000–2013, then uses the fixed-effects model to test a total of 410,326 samples of 114,897 enterprises. We empirically analyzed the impact of environmental regulations on the export products switching from the perspective of heterogeneity. We found that: the intensity of environmental regulations is positively correlated with the total switching rate of export products, the increase rate of export products and the export product obsolescence rate. Environmental regulations have a greater impact on the export products switching of general trade enterprises than on processing trade; the impact on private and foreign enterprises is greater than that on state-owned enterprises; the impact on high-tech enterprises is greater that than on low and medium-tech enterprises; through theoretical analysis and empirical test, this paper reveals the mechanism and its promotion effect of environmental regulations on the export products switching of heterogeneous Chinese enterprises, which provides theoretical and practical support for the enhancement of China’s export products international competitiveness and environmental improvement.