Abstract: The reactions of the tris(acetylacetonato)silicone(IV) cation (Si(acac)3+) with Na+-, Mg2+-, and Co2+-exchange forms of hectorite and montmorillonite have been investigated to understand better the formation process of clays pillared by silicic acid. In acetone as the solvating medium, Si(acac)3+ binds to the Na+- and Mg2+-clays with the desorption of only a small fraction (∼5%) of the initial exchange cation, suggesting that the complex binds as the ion pair [Si(acac)3+][Cl−]. With the Co2+-clays, however, the exchange cation is desorbed quantitatively, and Si(acac)3+ binding is accompanied by the formation of an acetone-solvated CoCl2 solution complex which helps to drive the ion-exchange reaction. Thus, Co2+-smectites react with Si(acac)3+ in acetone to produce homoionic Si(acac)3+ intercalates, whereas Na+- and Mg2+-smectites produce mixed-ion intercalates. The interlayer hydrolysis of Si(acac)3+ to silicic acid in the homoionic Si(acac)3+- and mixed-ion Na+/Si(acac)3+- and Mg2+/Si(acac)3+-exchange forms of montmorillonite films is diffusion controlled. In water as the solvating medium, the reaction of Si(acac)3+ with Mg2+- or Co2+-montmorillonite results in the desorption of the exchange cations on a time scale which is comparable to that observed for the solution hydrolysis of Si(acac)3+. Thus, the precipitation of silicic acid from aqueous solution competes strongly with the formation of interlayer silicic acid. With aqueous Na+-montmorillonite dispersions, however, a significant fraction of the exchange cations desorbed rapidly upon Si(acac)3+ binding, and the formation of interlayer silicic acid is favored over the precipitation of Si(OH)4.