Considering the two-way influence of water ecology and industrial structure, decompose and quantify the water ecological rigidity constraints into water environment constraints and water resources constraints, construct the evaluation system based on the theoretical framework of PSR, and analyze the spatio-temporal evolution characteristics of water ecological rigidity constraints of the Yangtze River Economic Belt from 2010 to 2021 by using the entropy weighting method, the method of catastrophe progression, and the kernel density estimation. Then, putting forward the types of zoning in the Yangtze River Economic Zone through K-means algorithm analysis to explore the rigid constraints of water ecology to force the path of industrial structure adjustment. The results indicate that: (1) the water ecological rigidity constraints show a decreasing trend, and the decreasing amplitude is upstream > downstream > midstream; (2) the water ecological rigidity constraints generally show the characteristic of “gradually decreasing from east to west”, and the degree of regional differences first decreases, then increases, and then decreases again; (3) it can be divided into six types, and the zoning results gradually change from the concentration in the medium-high type and high-high type to the concentration in the low-low type and medium-low type, and the rigidity constraint of water ecology is obviously improved. In light of the findings, the Yangtze River Economic Belt is divided into five types of development regions and further discusses that the industrial restructuring in different zones has different influencing effects on the regional socio-economic development, which provides suggestions for differentiated paths of water ecological protection and industrial restructuring.