To determine the initial rates and effects of silica in solution on the dissolution kinetics of smectite, short- and long-term batch experiments (0.5 hour to 30 days) were completed at three temperatures (T = 25, 50, and 75°C) using stock solutions pH adjusted by NaOH (pH = 12, 13, and 13.5) with varying initial silica concentrations (0, 30, 60, and 100 ppm). The following important characteristics were observed at pH = 12: (1) The concentrations of Al, Si, Mg, Fe, and Ti in solutions increase rapidly during the first ∼2 hours and reach steady state (equilibrium) within ∼5 days. (2) The concentration ratios of Al, Si, Fe, Mg, and Ti in solutions during the early (<2 hours) reaction phase differ significantly from those of smectite, indicating initial dissolution proceeds non-stoichiometrically; Al dissolves much faster than Si, Mg, Fe, and Ti. (3) Further dissolution of smectite proceeds nearly stoichiometrically, including Fe and Ti. (4) The high solubility of Ti in highly alkaline solutions may be due to the formation of aqueous complexes, such as TiO(OH)3− and TiO2(OH)22−, similar to aqueous silica species. (5) The initial rate of smectite dissolution increases with increasing pH, T, and initial silica content of solution. (6) The silica in solution acts as a promoter and a catalyst, rather than an inhibitor, of smectite dissolution in high-alkaline solutions. This role is easily recognizable when the solubility of smectite and amorphous silica are very high, i.e., at pH >∼9.