Catalytic activity of gamma-alumina supported rhodium catalysts in nitrous oxide decomposition into dinitrogen and dioxygen has been determined, the total conversion being reached at 450 degrees C. Rhodium is present at alumina surface in three forms: metal particles, Rh2O3 and rhodium zero valent atoms interacting with oxygen ions at the metal/support interface. Linear dependence of the catalytic activity on rhodium dispersion has been found. Deposition of alkali metal cations: Li, Na, K and Cs as promoters at the surface of alumina results in a considerable increase of rhodium dispersion and hence catalytic activity. The effect of promoters depends strongly on the speciation of alkali metals and rhodium used in the preparation of the catalyst. Both alkali metal cations and rhodium compete for the same OH groups at the alumina surface. The electronegativity of alkali metal oxides is much greater than that of alumina and their deposition increases the negative charge of surface oxide ions hindering the diffusion of rhodium and preventing the growth of its larger particles. (C) 2007 Published by Elsevier B.V.