In this study, a rapid freezing process was used to synthesize the three-dimensional graphene composite [Pt/3D GNs (C)] in which graphite oxide and K2PtCl4 were simultaneously reduced via refluxing at 90 A degrees C using ascorbic acid as a reducing agent and then were rapidly frozen in liquid nitrogen to obtain Pt/3D GNs (C). Due to the rapid freezing treatment in liquid nitrogen, an obvious wrinkled layer structure of graphene is formed, and the Pt nanoparticles in Pt/3D GNs (C) mainly exist in the form of flower nanoclusters with an average diameter of approximately 40 nm. The introduction of carbon black has no apparent effect on the morphologies of Pt nanoclusters on the wrinkled graphene surface, but carbon black can serve as a nano-spacer between Pt nanoclusters and graphene, giving rise to good contact of the Pt-C-graphene interfaces. Electrochemical tests show that Pt/3D GNs (C) exhibits superior activity, stability, and resistance to CO poisoning for catalyzing methanol oxidation as compared with Pt/3D GNs, Pt/GNs and commercial Pt/C-JM, which may derive from its better interface contact and stronger interaction between Pt and carriers, larger electrochemical active surface area, and higher content of oxygen-containing groups on the carrier surface. [GRAPHICS] .