The hybrid material of reduced graphene oxide (RGO)/phenol formaldehyde (PF) resol is synthesized and treated different time by microwave (MW) heating. Pt particles loaded on these RGO/PF substrates demonstrate remarkably enhanced specific activity (SA) to methanol oxidation reaction (MOR) in comparison with the commercial Pt/C. Among all the prepared catalysts, the one containing the RGO/PF with middle time of MW treatment shows highest SA value, more than three times of Pt/C. The surface analysis reveals that the RGO/PF with middle time of MW treatment contains highest content of total oxygen, carbonyl and carboxyl groups. Examining the data of surface analysis and MOR testing together, we inferred that the fine-tuned surface properties of supporting materials are the key role for the great enhancing of SA. Our results verify the crucial influence of substrate surface properties on the performances of Pt catalysts and provide a considerable way to develop high active and low cost catalysts for fuel cell. Copyright (C) 2016, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.