Rh/TiO2 catalysts have been prepared under different experimental conditions (namely, crystallographic phase of the support, Rh loading, incorporation method, etc.) and reduced at 773 K. Hydrogenolysis of n-butane has been used as a reaction test to characterize these catalysts. The reaction parameters (activation energy and frequency factor) have been determined and the change in selectivity to methane, ethane and propane has been studied following the Kempling-Anderson formalism.