Abstract: Industrial network is an important starting point to reflect the economic relations between cities. Urban agglomeration is an important carrying capacity of economic relations between cities. It is of great significance to clarify the spatial evolution characteristics and environmental effects of urban agglomeration industrial network for promoting the coordinated development, green development and sustainable development of urban agglomeration. Taking the urban agglomerations of Beijing-Tianjin-Hebei, the Yangtze River Delta and the Pearl River Delta as examples, this paper used ArcGIS spatial analysis and social network analysis to reveal the spatial evolution characteristics of the industrial network of the three major urban agglomerations, based on the enterprise investment behavior from 2011 to 2020. The spatial Durbin model was used to further explore the environmental effects of industrial networks. The findings were as follows: (1) The spatial pattern of industrial network in the Beijing-Tianjin-Hebei urban agglomerations was characterized by "one main axis, two centers and multiple vertices". The industrial network of the Yangtze River Delta urban agglomerations presented a spatial pattern of "one main and more auxiliary", and the phenomenon of "core-edge" and regional grouping were obvious. The spatial pattern of the industrial network of the Pearl River Delta urban agglomeration was characterized by "one main and two auxiliary", which gradually turned from "V" type to "inverted V" type. (2) The point entry degree of most central cities in the three major urban agglomerations was greater than the point exit degree, and the phenomenon of industrial agglomeration in central cities was obvious. (3) There was spatial heterogeneity in the environmental effect of enterprises' outbound investment. The outbound investment of enterprises in the Beijing-Tianjin-Hebei urban agglomerations significantly promoted the environmental governance of the region and its neighboring regions. The industrial network of the Pearl River Delta urban agglomerations had a significant spatial spillover effect on environmental governance, while the industrial network of the Yangtze River Delta urban agglomerations had no significant environmental effect. This research can provide decision-making reference for promoting the coordinated development of the three major urban agglomerations and the coordinated governance of the ecological environment.