Serious air pollution has occurred in China since 2012. With the increasing investment in technological innovation in China, the role of green technological innovation in reducing air pollution has attracted more and more attention. By constructing the spatial Durbin model and threshold regression model and using the statistical data of China’s provinces, this study explores the spatial effects and threshold characteristics of China’s green technology innovation on the environmental pollution of China’s air pollution-intensive industrial agglomeration. The research objective is to find out the spatial effects and threshold characteristics of green technology innovation on the environmental pollution of China’s air pollution-intensive industrial agglomeration. The results show that thermal power, etc., air pollution-intensive industrial are important sources of sulfur dioxide emissions; however, their degree of concentration is gradually increasing, resulting in rising sulfur dioxide emissions in these areas. When the level of green technological innovation is greater than 8.0523, its inhibition effect on sulfur dioxide emissions in these industries is significantly increased. Improving green technology innovation ability in thermal power, etc., air pollution-intensive industrial agglomeration areas can effectively reduce pollution in the atmosphere. The level of green technology innovation in key zones must be increased to adjust the concentration of pollution-intensive industries, improve China’s industrial structure, and reduce atmospheric environment pollution.