Under the increasing pressure of water shortage and steppe degradation, information on the hydrological cycle in the steppe region in Inner Mongolia is urgently needed. Major ions are widely used to identify the hydrological processes in a river basin. Based on the analysis results of 239 river water samples collected in 13 sections along the Xilin River system during 2006 to 2008, combined with data from groundwater and precipitation samples collected in the same period and the meteorological and hydrological data in the Xilin River Basin, hydrochemical characteristics and the chemistry of major ions of the Xilin River water have been studied by means of Piper triangle plots and Gibbs diagrams. The results showed that: (1) the total dissolved solid (TDS) in river water mainly ranged between 136.7 mg x L(-1) and 376.5 mg x L(-1), and (2) it had an increasing trend along the river flow path. (3) The major cations and anions of river water were Ca2+ and HCO3-, respectively, and the chemical type of the river water varied from HCO3- -Ca2+ in the headwater area to HCO(3-)-Ca2+ Mg2+ in the lower part. (4) The variation in the concentration of major irons in surface water was not significant at the temporal scale. Usually, the concentration values of major irons were much higher in May than those in other months during the runoff season, while the values were a bit lower in 2007 than those in 2006 and 2008. Except for SO4(2-), the concentrations of other ions such as Ca2+, Na+, Mg2+, K+, Cl- and HCO3- showed a upward trend along the river flow path. Comparing major ion concentrations of the river water with those of local groundwater and precipitation, the concentration in river water was between those of precipitation and groundwater but was much closer to the concentration of groundwater. This indicated that the surface water was recharged by a mixture of precipitation and groundwater, and groundwater showed a larger impact. The Gibbs plot revealed that the chemical compositions of the river water were mainly affected by rock weathering in the drainage area.