The dissolution of kaolinite in aqueous solutions of hydrofluoric acid was investigated at different temperatures and fluoride concentrations. The percentage dissolution of kaolinite was greater than was to be expected from a theoretical consideration of the reaction. The percentage dissolution was less for Na‐kaolinite than for a H‐kaolinite under the same experimental conditions. Two reaction rates were observed. The relative intensities of the 001 and 002 basal reflections decreased with reaction time, temperature and hydrofluoric acid concentration. The decrease was probably due to an amorphous phase. Although kaolinite samples after treatment at the lower temperature showed very little change in their infra‐red absorption spectra, a marked change in the spectra was observed at the higher temperature. The disruption of the kaolinite crystal lattice is believed to be due to the preferential extraction of aluminium from the lattice leaving an intermediate silica phase, which dissolves to form fluorosilicic acid.