Abstract: Unreasonable industrial structure and layout are the main causes of serious air pollution in Beijing-Tianjin-Hebei and surrounding areas. The optimization of regional industrial structure and layout can effectively improve the quality of regional atmospheric environment. The industrial structure similarity coefficient method, the industrial structure deviation correction index method and the industrial structure transfer measurement method were applied to quantitatively assess the degree of convergence, rationalization and advancedization of the industrial structure of the seven provinces (autonomous regions, municipalities) in Beijing-Tianjin-Hebei and surrounding areas. According to the requirements of regional atmospheric environmental quality improvement, the countermeasures for industrial structure optimization were proposed. The results showed that the similarity coefficient of industrial structure between Beijing, Tianjin and Hebei and the surrounding provinces had been increasing year by year and close to 1, and there was a serious structural convergence phenomenon. Except for Beijing, the rationalization degree of industrial structure in other provinces was generally low, and the improvement rate was slow. The advancedization degree of regional industrial structure was on a gradual upward trend. Beijing’s industrial structure was the most advanced and other provinces were generally lower. In the future, measures should be taken to improve the regional industrial structure, including clarifying the development characteristics and positioning of each province formulating differentiated development strategies, optimizing industrial layout as a whole and accelerating industrial transfer and integration.