This study aims to investigate hydrogeochemical characteristics and groundwater quality in the Hebei Plain and to discuss factors controlling the groundwater quality. A total of 54 groundwater samples were collected and analyzed for 31 hydrogeochemical parameters, and a fuzzy synthetic evaluation (FSE) method was used for assessing groundwater quality. Results show groundwater total hardness, total dissolved solids (TDS), and major ions excluding K+ in phreatic aquifers higher than that in confined aquifers. From the Piedmont plain to the littoral plain, phreatic aquifers towards the reducing environment, and the enhancement of water–rock interaction, ion exchange process, and evaporation probably resulted in the increase in groundwater TDS, major ions (excluding HCO3− and SO42−), B, and Mn concentrations. Moreover, phreatic groundwater chemistry was mainly controlled by rock weathering changing into evaporite dissolution and seawater intrusion from the Piedmont plain to the littoral plain, according to the Gibbs diagram. The proportion of drinkable groundwater in confined aquifers was 1.6 times that in phreatic aquifers. In phreatic aquifers, the proportion of drinkable groundwater in the Piedmont plain was as high as 68%, but none of the drinkable groundwater occurred in the central and littoral plains. Groundwater quality in phreatic aquifers was mainly controlled by five factors, including the water–rock interaction, the marine geogenic sources, the agricultural pollution, the acidification, and the reductive environment. By contrast, groundwater quality in confined aquifers was mainly controlled by three factors, including the water–rock interaction and redox processes, agricultural pollution, and the input of external water. Therefore, in the Hebei Plain, groundwater in confined aquifers is more suitable for drinking purposes than in phreatic aquifers. Additionally, phreatic groundwater in the Piedmont plain should be protected.