A 20-m-wide trench was excavated to bedrock on a hillslope at the Panola Mountain Research Watershed in the Piedmont region of Georgia to determine the effect of upslope drainage area from the soil and bedrock surfaces on the geochemical evolution of base cation concentrations in subsurface flow. Samples were collected from ten 2-m sections and five natural soil pipes during three winter rainstorms in 1996. Base cation concentrations in hillslope subsurface flow were generally highest early and late in the storm response when flow rates were low, but during peak flow, concentrations varied little. Base cation concentrations in matrix flow from the 10 trench sections were unrelated to the soil surface drainage area and weakly inversely related to the bedrock surface drainage area. Base cation concentrations in pipe flow were lower than those in matrix flow and were also consistent with the inverse relation to bedrock surface drainage area found in matrix flow. The left side of the trench, which has the highest bedrock surface drainage area, had consistently lower mean base cation concentrations than the right side of the trench, which has the lowest bedrock surface drainage area. During moderate size rain events of about 20–40 mm, subsurface flow occurred only on the left side of the trench. The greater volume of water that has flowed through the left side of the trench appears to have resulted in greater leaching of base cations from soils and therefore lower base cation concentrations in subsurface flow than in flow from the right side of the trench. Alternatively, a greater proportion of flow that bypasses the soil matrix may have occurred through the hillslope on the left side of the trench than on the right side. Flushing frequency links spatial hillslope water flux with the evolution of groundwater and soil chemistry.