Effects of particle size of Cr2O3 catalyst on the hydrogen absorption/desorption kinetics of Mg + 5 wt% Cr2O3 mixtures have been studied. To explain the effect of particle size of Cr2O3 and also to yield information about the role of Cr2O3 during the sorption process, the kinetics data have been analyzed using Avrami–Erofeev rate equations. The activation energies and diffusion coefficients of these mixtures are in the ranges of 50.6–63.2 kJ/mol and 1.2.10−11 to 8.9.10−10 cm2/s, respectively. The addition of nano-oxides led to an increase of the diffusion coefficient of hydrogen by one order of magnitude.