In this work, Pt-SiO2/graphene nanocomposites have been synthesized under solvothermal conditions and investigated as electrocatalysts for methanol oxidation. Structure and morphology of these catalysts are characterized by transmission electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and nitrogen adsorption/desorption studies. The Pt and SiO2 contents of these nanocomposites are determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Their electrocatalytic properties are investigated by cyclic voltammetry, chronoamperometry, chronopotentiometry and electrochemical impendence spectroscopy. The as-prepared nanocomposites show the improved catalytic performance, better stability and good antiposoining ability compared with Pt supported on graphene catalyst. Particularly, the catalyst containing 9.24% of SiO2 exhibits the best electrocatalytic performance for methanol oxidation with mass activity of 1047mAmg−1.