A novel tri-component hybrid, Pt/pyridine ionic liquid polyoxometalate/reduced graphene oxide denoted as Pt/(epy)(3)PMo12O40/rGO with well-dispersed, smaller size Pt nanoparticles on rGO is successfully synthesized. The morphology, structure, composition and electrochemical property are characterized by high resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive spectrometer, Raman spectra, thermogravimetric analysis and cyclic voltammetry, respectively. Ionic liquid polyoxometalate (epy)(3)PMo12O40 availably prevents the aggregations of Pt nanoparticles on the rGO surface, furthermore, effectively improves anti CO poisoning performance and enhances the conductivity of the material. The mass activity of as-prepared Pt/(epy)(3)PMo12O40/rGO catalyst for methanol oxidation is about 10 times of 20% commercial platinum carbon, 7 times of Pt/ rGO, 4 times of Pt/epyBr/rGO, and 2 times of Pt/H3PMo12O40/rGO. This further demonstrates that the ionic liquid polyoxometalate (epy)(3)PMo12O40 play a very important role in enhancing the eletrocatalytic activity of the tri-component hybrid composite catalyst. (C) 2018 Published by Elsevier Ltd.