This research examines the spatial agglomeration characteristics of industrial enterprises and their spatial coupling characteristics with water pollution discharge in Zhangjiakou by the method of kernel density analysis and pollutant discharge intensity, based on the environmental statistical data of industrial pollution sources in the study area. The results show that: (1) There is a certain spatial heterogeneity in the spatial concentration of industrial enterprises, and there is almost no pollution-intensive enterprise in Chongli and Chicheng counties. Pollution-intensive enterprises mainly distribute in the urban ecological construction functional areas along the Yanghe River. (2) Agricultural and sideline food processing industry, ferrous metal smelting and calendaring processing industry, food manufacturing industry, coal mining and washing industry are the four major industries with the largest discharge of water pollutants such as COD, NH3-N and total nitrogen. (3) The spatial positive coupling effect between the degree of industrial enterprise agglomeration and the degree of water pollution is obvious, and 96.23% of the areas show a strong positive coupling. The proportion of high pollution value-high concentration area was 0.40%. In view of the four spatial coupling types, the future direction of pollutant emission control is proposed in order to provide the decision-making basis for the government to accurately lock the control area.