The catalytic properties of three supported platinum catalysts, 0.75 wt% Pt/SiO2, 0.89 wt% Pt/Al2O3, and 0.48 wt% Pt/MoO3, are reported for the hydrogenolysis of ethane, propane, n-butane, and iso-butane. The reactions were carried out in a flow reactor at atmospheric pressure. The apparent activation energies, E-app, for the hydrogenolysis reactions and the isomerisation reactions of n-butane and iso-butane, all show a compensation effect with the corresponding values of In A(app). This compensation effect can be accounted for by the dehydrogenative chemisorption of the alkanes as the first step in the reaction mechanisms to both hydrogenolysis and isomerisation. No apparent structure sensitivity was demonstrated by the three catalysts for the hydrogenolysis of ethane. The Pt/Al2O3 catalyst showed the highest activity of the three catalysts for the hydrogenolysis of propane. This high activity can be related to the strong adsorption of alkane fragments on platinum sites on the Pt/Al2O3 catalyst which exhibit delta+ polarisation. Over the Pt/SiO2 and Pt/Al2O3 catalysts the isomerisation of n-butane and iso-butane can be explained by a metal-only catalysed isomerisation route, Very high levels of isomerisation over the Pt/MoO3 catalyst agree with a bifunctional mechanism involving acid sites on the MoO3 support.