With the rapid development of urbanization, the chemical evolution of groundwater has been significantly affected by human activities. However, the driving mechanisms of groundwater chemical evolution at different stages of urbanization are still unclear, which severely affects the implementation of groundwater protection. This study investigated the driving mechanisms of groundwater chemical evolution based on the long-term series (from 1985 to 2015) of hydrochemical data from 19 groundwater monitoring sites in rapidly urbanizing areas (Shijiazhuang, Hebei Province, China). The results show that the concentrations of various chemical components in groundwater gradually increase with the acceleration of the urbanization process, especially NO3−, which has increased from 13.7 mg/L in the primary stage of urbanization (PSU) to 65.1 mg/Lin the advanced stage of urbanization (ASU), exceeding the World Health Organization (WHO) drinking water standard (50 mg/L), indicating that the groundwater chemistry has been significantly affected by human activities. The main hydrochemical types have changed from the HCO3•SO4-Ca•Mg-type water in the primary stage of urbanization (PSU) to the SO4•HCO3-Ca•Mg-type water in the advanced stage of urbanization (ASU). It is worth noting that there are obvious differences in driving factors of groundwater chemical evolution at different urbanization stages. In the primary stage of urbanization (PSU), the driving factors were carbonate and rock salt dissolution, cation exchange, and industrial activities. However, in the intermediate stage and advanced stage, the driving factors were changed to carbonate and gypsum dissolution, groundwater over-exploitation, agricultural fertilization, and domestic sewage. Based on the above conclusions, it is suggested that future groundwater management should control the amount of agricultural fertilizers, apply scientific fertilization, and prohibit the discharge of various types of non-compliant sewage, while strengthening the supervision of groundwater extraction to reduce the impact of urbanization development on the groundwater chemical evolution process.