With the implementation of the policy of ecological protection and high-quality development of the Yellow River Basin, the Guohe River Basin, which is close to the middle reaches of the Yellow River Basin, is also an important part of future development. Mathematical statistics, the Piper diagram, ion proportion coefficient method, Gibbs diagram and reverse hydrogeochemical simulation are used to analyze the chemical characteristics and evolution of groundwater in the Guohe River Basin (Henan Section). The dominant ions in the study area are HCO3− and Na+, and the three-layer aquifer has obvious zoning characteristics. The results show that the chemical types of shallow groundwater in this area are HCO3−Na • Mg • Ca, intermediate HCO3-Na and deep HCO3−Na. Using the ion proportion coefficient method, it is found that Na+, Ca2+, and Mg2+ in the groundwater aquifer undergo cation exchange in the aquifer. According to the reverse hydrogeochemical simulation, gypsum in the three aquifers is in a dissolved state, carbonate and sulfide ores in the shallow layer are dissolved, dolomite and halite in the intermediate layer are dissolved, calcite and sulfide ores are precipitated and carbonate, halite and sulfide ores in the deep layer are precipitated; the hydrogeochemical evolution model is established to find that Ca2+ in groundwater displaces Na+ in the aqueous medium. This research can provide a scientific basis for the rational development and utilization of groundwater and ecological protection in the Yellow River Basin.