The Heihe River Basin is a typical arid inland river basin for examining stress on groundwater resources in northwest China. The basin is composed of large volumes of unconsolidated Quaternary sediments of widely differing grain size, and during the past half century, rapid socio-economic development has created an increased demand for groundwater resources. Understanding the hydrogeochemical processes of groundwater and water quality is important for sustainable development and effective management of groundwater resources in the Heihe River basin. To this end, a total of 30 representative groundwater samples were collected from different wells to monitor the water chemistry of various ions and its quality for irrigation. Chemical analysis shows that water presents a large spatial variability of chemical facies (SO4 (2-)-HCO (3) (-) , SO4 (2-)-Cl-, and Cl--SO4 (2-)) as groundwater flow from recharge area to discharge area. The ionic ratio indicates positive correlation between the flowing pairs of parameters: Cl- and Na+(r = 0.95), SO4 (2-) and Na+ (r = 0.84), HCO3 (-) and Mg2+(r = 0.86), and SO4 (2-) and Ca2+ (r = 0.91). Dissolution of minerals, such as halite, gypsum, dolomite, silicate, and Mirabilite (Na2SO4 center dot 10H(2)O) in the sediments results in the Cl-, SO4 (2-), HCO3 (-), Na+, Ca2+ and Mg2+ content in the groundwater. Other reactions, such as evaporation, ion exchange, and deposition also influence the water composition. The suitability of the groundwater for irrigation was assessed based on the US Salinity Laboratory salinity classification and the Wilcox diagram. The results show that most of the groundwater samples are suitable for irrigation uses barring a few locations in the dessert region in the northern sub-basin.