In this paper, an efficient catalytic route for the reduction of graphene oxide (GO) is described using hydrogen spillovered platinum (Pt) nanoparticles at room temperature. Pt nanoparticles were decorated on GO sheets using a hydrogen reduction of chloroplatinic acid. The Pt nanoparticles served as a catalyst for the process of hydrogen disassociation to atomic hydrogen, which spillovered onto the GO sheets which acted as a strong reducing agent for the reduction of GO. Reduced graphene oxide (RGO) obtained in this manner has a C/O atomic ratio as high as 22, which is one of the highest values ever reported for chemically converted graphenes. The electrical conductivity was greater than 8000 S m−1. Electrochemical studies revealed that the RGO–Pt hybrid exhibits excellent electrocatalytic activity toward the methanol oxidation reaction, with high CO tolerance and long-term stability.