Precise information on the location of charge in clay minerals and their charge density in smectite-dominant soils is rare. The present study was undertaken with three benchmark Vertisols to establish the relationship between the clay cation exchange capacity (CEC), charge density, as well as the location of charge in smectitic soil clay minerals and their relationship with potassium (K) fixation and release. Potassium fractions and their threshold levels in the Vertisols were determined by standard methods. Soils were segregated into silt, total clay and fine clay fractions for X-ray diffraction analysis and fine clay fractions were used to determine the CEC using standard methods. The Hofmann-Klemen effect (HK) and modified Greene-Kelly test was done with the fine clay to determine the CEC of the tetrahedral sheet. Subsequently, the CEC of the octahedral sheet was calculated as the difference between total CEC and the tetrahedral CEC. The results showed that ~60–64% of the total CEC is attributed to the tetrahedral layers. The tetrahedral CEC that is proportional to the tetrahedral charge density was significant and negatively correlated with K release threshold values and all fractions of K. The tetrahedral CEC contributed more toward the K fixation and release than the octahedral CEC. The study shows that the dominant presence of high-charge smectites in the fine clay fractions of these Vertisols contributed to the tetrahedral CEC and consequently to the charge density of these soils, which implied a tendency to fix K easily and release it with greater difficulty compared to soils with low-charge smectites.