To explore the chemical characteristics and environmental factors of groundwater in the Hetao Irrigation Area of Inner Mongolia, five irrigation fields, including UulanBuh, Jiefangzha, Yongji, Yichang, and Wulat, were selected as the research area. From 72 groundwater observation wells, a total of 216 groundwater samples were collected throughout three typical periods: the end of freeze-thaw (March), the middle of irrigation (July), and the end of autumn watering (November). Comprehensive methods were utilized, such as statistical analysis, Piper three-line diagram, Gibbs diagram, ion ratio, and principal component analysis, to explore the changes in the groundwater chemical environment and the environmental driving factors of groundwater component formation. The groundwater drinking suitability was evaluated using the water quality index (WQI), and the irrigation suitability was analyzed using the USSL and Wilcox plots. The results indicated that the groundwater in the research areas was generally saline, and the total anion and cation concentrations in each period in ascending order were as follows: late freeze-thaw stage, late autumn irrigation stage, and mid-irrigation stage, with Na+ and Cl- being the major contributing ions. The chemical type of groundwater was dominated by Cl-Na, followed by Cl·SO4-Ca·Mg and a coexistence with SO4-Ca·Mg, HCO3·Cl-Na, HCO3-Na, and HCO3-Ca·Mg. Based on WQI values, the shallow groundwater in Hetao Irrigation District was mainly classified as Class IV and Class V, and the quality was poor in general. According to the USSL diagram and Wilcox diagram, the comprehensive evaluation results showed that the salinity and sodium concentration of shallow groundwater in the irrigation area were generally high. A total of 80.6% of the water samples during the late freeze-thaw period, 76.1% during the mid-irrigation period, and 77.6% during the late autumn irrigation period lacked irrigation suitability. Two major controlling factors of groundwater chemical characteristics were present in the study area, namely, evaporation and rock weathering, and Na+ and Cl- mainly came from the dissolution and cation exchange of salt rocks. Agricultural irrigation and drought were the chief driving factors of groundwater chemical evolution in the Hetao Irrigation Area. The study provides technical support for optimizing agricultural management measures and a theoretical reference for rational utilization of groundwater resources in the Yellow River irrigation area of Inner Mongolia.