Catalytic action of the system based on platinum and heteropoly compound (HPC) was studied in the oxidation of cyclohexane with O-2/H-2 gases to produce cyclohexanol and cyclohexanone. The active composition was represented by a solid bi-component catalyst prepared from the [Pt(NH3)(4)][H2PMo12O40](2).7H(2)O complex salt through calcination and redox treatments. The bi-component catalysts were characterized by HREM, XPS, and IR spectroscopy. The active samples consisted of undestroyed crystalline HPC with finely dispersed Pt species, which contained both metallic and ionic states. Reversible Mo6+/Mo5+ electron transfer in HPC was easily realized under conditions of catalytic reaction. Based on the state of the active catalysts, a scheme of O-2/H-2 activation and cyclohexane oxidation was suggested. According to the scheme, oxidation proceeded via radical hydroxyl intermediate.