The cation exchange capacity (CEC) of the clay fraction (<2 μm), denoted as CECclay, serves as a crucial indicator for identifying low-activity clay (LAC) soils and is an essential criterion in soil classification. Traditional methods of estimating CECclay, such as dividing the whole-soil CEC (CECsoil) by the clay content, can be problematic due to biases introduced by soil organic matter and different types of clay minerals. To address this issue, we introduced a soil pedotransfer functions (PTFs) approach to predict CECclay from CECsoil using experimental soil data. We conducted a study on 122 pedons in South China, focusing on highly weathered and strongly leached soils. Samples from the B horizon were used, and eight models and PTFs (four machine learning methods, multiple linear regression (MLR) and three PTFs from publication) were evaluated for their predictive performance. Four covariate datasets were combined based on available soil data and environmental variables and various parameters for machine learning techniques including an artificial neural network, a deep belief network, support vector regression and random forest were optimized. The results, based on 10-fold cross-validation, showed that the simple division of CECsoil by clay content led to significant overestimation of CECclay, with a mean error of 14.42 cmol(+) kg−1. MLR produced the most accurate predictions, with an R2 of 0.63–0.71 and root mean squared errors (RMSE) of 3.21–3.64 cmol(+) kg−1. The incorporation of environmental variables improved the accuracy by 2–10%. A linear model was fitted to enhance the current calculation method, resulting in the equation: CECclay = 15.31 + 15.90 × (CECsoil/Clay), with an R2 of 0.41 and RMSE of 4.48 cmol(+) kg−1. Therefore, given limited soil data, the MLR PTFs with explicit equations were recommended for predicting the CECclay of B horizons in humid subtropical regions.
