In order to study the chemical evolution mechanism of the underground water in the Jiaozuo mining district and ascertain the recharge sources of karst water to provide scientific evidence for the prevention of mine water bursting, water from the study areas is sampled. It is discovered that the exchange of positive ions of Ca2+-Na+ and Mg2+-Na+, efflorescence and lioxiviation evaporation and concentration, non-congruent dissolution of dolomite are the major hydrological and chemical process to control the formation and the evolution of the underground water, which provides a theoretical basis to infer the recharging sources of groundwater in the mining district.