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Forty‐four soil clays and four reference phyllosilicate clays were used to establish qualitative and quantitative relationships between clay mineral characteristics and K fixation. The soil clays were obtained from Vertisols, Vertic Mollisols, Haploxerolls, Xerochrepts, and a Palexeralf, from three semiarid regions of northwestern Morocco. The soil clays contained beidellite, montmorillonite, vermiculite, and illite in widely varied abundances. Both total and tetrahedral cation‐exchange capacity (CEC) were measured. Octahedral CEC was calculated by difference. Tetrahedral CEC was determined after saturation with Li and heating at 300 °C to reduce octahedral charge to near zero. Potassium fixation was determined in both wet (1:4 soil/solution, 16 h on a shaker) and dry conditions (after drying for 24 h at 70 °C) using three different levels of added K. Total CEC was well correlated with tetrahedral CEC (r2 = 0.76, P < 0.001). About half of the smectitic and vermiculitic soil clays have >50% of their total charge due to tetrahedral charge. The amount of K fixed Increased with added K, whereas the percent K fixed relative to total added K decreased. The K fixation by the clays studied was best correlated with total CEC for a given amount of K added. It was also well correlated with tetrahedral CEC. Simple regression analysis did not show any significant effect of octahedral CEC. A multiple regression analysis, however, demonstrated that both components of total CEC, tetrahedral and octahedral, have a simultaneous effect on K fixation. Tetrahedral CEC explained more of the variation (64%) than octahedral CEC (36%). This greater effect was attributed mainly to the proximity of tetrahedral charge to the interlayer space of 2:1 phyllosilicate clays.