In order to reveal the temporal and spatial evolution of water use structure in Hebei Province, information entropy theory was employed to analyze the spatio-temporal characteristics of water use structure in cities of Hebei Province from 2001 to 2018. The results showed that the information entropy of water use structure in various cities of the province increased from 0.68 to 1.00, which reflected an increase of stability and balance in the water use system. On the temporal scale, cities within the province were categorized as “high-level”, “medium-level” and “low-level” according to the information entropy values, and the discrepancies of different levels were gradually enlarging, and the difference of the information entropy between any two levels was larger than 0.12 in 2018. The spatial distribution of information entropy in Hebei Province illustrated a gradual variation, which decreased from the Bohai Rim to the inland and from the Beijing-Tianjin Rim to the southern Hebei. The above spatio-temporal evolution characteristics of information entropy reflected the influence of economic and social development on the variation of water use structure. The findings could provide some technical support for the effective decision-making of industrial optimization and local water resources management in Hebei Province.