Soil cation exchange property (SCEP) is important in soil development and environmental buffering. However, the variations in SCEP and its correlation with soil-forming factors in subsurface soil are not fully understood. In this study, we quantified the surface and subsurface SCEP variations as a function of parent material, vegetation, hillslope position, and soil type. Fifty upland soil profiles from mid-subtropical China were selected. The cation exchange capacity (CEC) and effective CEC (ECEC) of subsurface soil were significantly higher in soils derived from slate, Quaternary red clay (QRC), and limestone than in soils derived from granite and sandstone. The subsurface soils derived from limestone had the highest base saturation (BS) and the sum of base cations, and the lowest aluminum (Al) saturation. The SCEP in surface soil significantly varied with vegetation and hillslope position. The surface soil CEC was the highest in mixed-forest vegetation, whereas the ECEC and exchangeable acidity (EA) were the highest in arable vegetation. Exchangeable potassium (K+) was lowest and the EA was highest in soil orders at the strong development phase. Exchangeable calcium (Ca2+), magnesium (Mg2+), CEC, and BS were the highest in soil orders at the intermediate development phase. The prediction accuracy of soil CEC using the random forest model was higher than that obtained using multiple stepwise regression, with the best results (R2 = 0.92) obtained in the surface soil. Our study indicated that the SCEP in surface and subsurface soils was controlled by different soil-forming factors and could be effectively predicted by soil properties in subtropical China.