With the growth of China’s economy, environmental pollution has become more serious. Heavy polluting industries received more attention due to their high pollution and high-energy production methods. This paper studied the impact of industrial agglomeration of heavily polluting industries on the environmental performance, which can help realize the sustainable development of China’s economy and environment. In this paper, the employment number of heavily polluting industries in 30 provinces from 2013 to 2017 was selected, and the location quotient method was used to measure the industrial agglomeration of the heavily polluting industries. For the explained variable, environmental performance, this paper used the DEA-SBM method and selected an inseparable undesired output model to measure. In addition, the panel data were chosen for descriptive analysis, and the Z-score method was used to standardize the data. Then the correlation analysis and multiple linear regression analysis were conducted on the standardized data, mainly to study the impact of industrial agglomeration of heavily polluting industries on provincial environmental performance. Research results showed that the agglomeration degree of heavily polluting industries has a U-shaped influence on environmental performance. Finally, this paper proposed viable suggestions from three aspects: government, society, and industry.