The catalytic properties of model Pt/SiO2 and Pt/Al2O3 catalysts and their physical mixtures with SO4/ZrO2 in the reaction of n-hexane isomerization have been studied. Significant effects of the influence of the platinum state on the characteristics of isomerization on the catalysts and their physical mixtures with SO4/ZrO2 have been revealed. The observed changes in catalytic performance of the mixed catalysts have been explained from the position of a bifunctional mechanism with the participation of ionic platinum promoting the formation of hydride ions, which play an important role in the activation of transformations of intermediates in isomerization reactions.