Developing green trade under the background of high-level opening-up is an inevitable choice for China’s economic transformation and upgrading, as well as achieving high-quality development. As a representative of green trade, the liberalization of environmental goods trade as an important path to achieve sustainable development has been widely recognized by countries around the world. As a major member of the World Trade Organization (WTO), China has fully participated in the negotiations of the Environmental Goods Agreement of WTO and actively developed the import trade of environmental goods. The import of environmental goods in China shows characteristics of first increasing in scale and then decreasing, imbalanced structure, and relatively fixed market. Combining Grossman and Krueger’s classic theories on trade and environment, as well as Antweiler’s general equilibrium model, this study theoretically explains the mechanism by which environmental goods import affects corporate pollution emissions. Panel data from micro enterprises in China are selected to empirically examine the environmental effects of environmental goods import. Research has found that firstly, importing environmental goods can reduce corporate pollution emissions. Further mechanism testing results indicate that the scale effect of environmental good imports increases the smoke and dust emissions of enterprises, while the technical effect reduces the smoke and dust emissions, and the composition effect is not significant. Secondly, in the subdivision of environmental goods, the import of resource management goods and clean technologies and goods has a significant effect on reducing enterprise smoke and dust emissions, while pollution management goods have no significant effect on environmental improvement. Thirdly, the increase in the import volume of environmental goods has a significant inhibitory effect on the emission of smoke and dust in state-owned enterprises, foreign-funded enterprises and high-polluting industries, while it has no significant effect on private enterprises and non-high-polluting industries. In view of this, it is suggested to establish international high standard economic and trade rules and institutional system, adhere to high-level “import” and implement import differentiation strategy, give full play to the role of the government and market in opening up to the outside world, and accelerate the cultivation of enterprises’green technology innovation capabilities, create an internationally first-class business environment, and implement the strategy of high-quality development to promote the construction of a trader of quality.