Previous studies have shown that shallow groundwater in arid regions is often not in equilibrium with near-surface boundary conditions due to human activities and climate change. This is especially the case where the unsaturated zone is thick and recharge rate is limited. Under this nonequilibrium condition, the unsaturated zone solute profile plays an important role in estimating recent diffuse recharge in arid environments. This paper combines evaluation of the thick unsaturated zone with the saturated zone to investigate the groundwater recharge of a grassland in the arid western Ordos Basin, NW China, using the soil chloride profiles and multiple tracers (2H, 18O, 13C, 14C, and water chemistry) of groundwater. Whereas conventional water balance and Darcy flux measurements usually involve large errors in recharge estimations for arid areas, chloride mass balance has been widely and generally successfully used. The results show that the present diffuse recharge beneath the grassland is 0.11–0.32 mm/year, based on the chloride mass balance of seven soil profiles. The chloride accumulation age is approximately 2,500 years at a depth of 13 m in the unsaturated zone. The average Cl content in soil moisture in the upper 13 m of the unsaturated zone ranges from 2,842 to 7,856 mg/L, whereas the shallow groundwater Cl content ranges from 95 to 351 mg/L. The corrected 14C age of shallow groundwater ranges from 4,327 to 29,708 years. Stable isotopes show that the shallow groundwater is unrelated to modern precipitation. The shallow groundwater was recharged during the cold and wet phases of the Late Pleistocene and Holocene humid phase based on palaeoclimate, and consequently, the groundwater resources are nonrenewable. Due to the limited recharge rate and thick unsaturated zone, the present shallow groundwater has not been in hydraulic equilibrium with near-surface boundary conditions in the past 2,500 years.