In recent years, people have realized the importance of corporate environmental responsibility. In this study, we combine the Slack-based Measurement (SBM) model with the "Super-efficiency" model to construct the environmental performance evaluation based on Data Envelopment Analysis (DEA) to measure the environmental performance of China's large iron and steel enterprises from 2009 to 2017. Then, it studies the impact of environmental performance on enterprise economic performance through regression analysis. The results show that the impact of environmental performance of China's large iron and steel enterprises on economic performance shows an inverted U-shaped relationship. The conclusion is helpful to encourage enterprises to actively carry out environmental management, so as to maintain and enhance the competitiveness of enterprises. Therefore, this paper suggests that iron and steel enterprises should balance the relationship between environmental responsibility and economic performance in order to maximize enterprise performance. The main purpose of this paper is to let enterprises solve the negative externalities in production through internalization, and encourage enterprises to adopt environmental protection behavior for production and operation.