The effect of the addition of alkali metals to Pt/Al2O3 catalysts for dehydrogenation of paraffins was studied. Results can be interpreted in terms of different effects. Thus, the addition of alkali metals produces a poisoning of the acid sites of the alumina support and a modification of the characteristics of the metallic phase. The latter effect involves not only an increase of the Pt particles size, but also an electronic modification of the metallic phase. These two effects are more marked with alkali metals with higher ionic radius, such as K.