A three-dimensional interconnected graphene monolith was used as an electrode support for pulsed electrochemical deposition of platinum (Pt) nanoparticles. Pt nanoparticles with well-defined morphology and small size can be obtained by controlling electrodeposition potential and time. Electrochemical characterization was carried out to examine the electrocatalytic activity of this monolithic electrode towards methanol oxidation in acidic media. The results show that the carbon material surface and structure have a strong influence on the Pt particle size and morphology. Compared with the three-dimensional scaffold of carbon fibers, the three-dimensional graphene when used as a free-standing electrode support resulted in much improved catalytic activity for methanol oxidation in fuel cells due to its three-dimensionally interconnected seamless porous structure, high surface area and high conductivity.