The diffusion rates of Na+ and Cs+ in two types of hydrous titanium(IV) oxide, precipitated at pH 6 (exchanger A) and pH 13 (exchanger B), were determined radiochemically. The rate of Cs+ in exchanger A is faster than that of Na+; diffusion coefficients are 4.9xl0-11 and 1.9xl0-11 m2 s-1 for Cs+ and Na+, respectively (pH 12, 5.0 °C). The activation energy for Cs+ diffusion is 21 kJ mol-1 and slightly smaller than that for Na+ diffusion, 29 kJ mol-1. The rates of these ions in exchanger B are much slower than those in exchanger A, and can be explained by assuming the existence of two kinds of independently diffusing ions (fast and slow species) in the exchanger. The diffusion coefficients are of the order of 10-12 and 10-13 m2 s-1 for the fast and the slow species, respectively. The activation energies are 48–60 kJ mol-1 for Na+ diffusion and 32–33 kJ mol-1 for Cs+ diffusion (pH 12). The marked difference in kinetics between two exchangers was interpreted in terms of the difference in the acid-base property and in the microstructure of the matrix.