We report a graphene three-dimensional network (G3DN) structure on a Si substrate, which is used as Pt nanoparticle support for effective electrocatalytic oxidation of methanol and ethanol. The controllable Pt loading on the G3DN is conducted by a facile, repeatable and environmentally friendly approach. The influence of graphene architecture on electrocatalytic activities is comparatively investigated by loading the same amount of Pt on the G3DN and on commercial graphene sheets (CGS). The Pt/G3DN (0.01 mg(Pt) cm(-2)) electrode exhibits a tremendous electrocatalytic activity for the oxidation of methanol and ethanol with oxidation current of 910.11 mA mg(Pt)(-1) and 246.69 mA mg(Pt)(-1) respectively owing to its high density of three-dimensional active sites, wavy sheet-network channels and synergistic effect of Pt and graphene. The peak current density ratio of the forward to backward potential scan is 2.79 and 0.65 for the methanol and ethanol oxidation respectively. The results reveal excellent characteristics of the Pt/ G3DN electrode, such as easy preparation, high catalytic activity, stability and tolerance toward poisoning effects for the electrooxidation of methanol. (C) 2014 Elsevier B.V. All rights reserved.