The Vulcan carbon-supported vanadium oxide (V₂O₅) was prepared by solid-state reaction under intermittent microwave heating (IMH) method. Pt nanoparticles were dispersed by microwave-assisted polyol process over Vulcan carbon and V₂O₅/C. The catalyst samples were characterized by PXRD, TEM, CO-TPD and electrochemical methods. The TEM images showed homogeneous dispersion of ∼3nm size Pt metal crystallites embedded over Vulcan carbon support. The activities of Pt/C and Pt–V₂O₅/C for electrochemical oxidation of methanol were studied in 1.0M KOH solution by cyclic voltammetry, chronoamperometry and chronopotentiometry. The influence of V₂O₅ component on the activity of Pt–V₂O₅/C was screened for catalytic oxidation of methanol. The results show that Pt–V₂O₅(4:3)/C composite catalyst performed better than Pt/C catalyst for methanol oxidation. The temperature programmed desorption (TPD) with CO was carried out to assess the CO tolerance of Pt–V₂O₅/C electrocatalyst. The formation of oxygen-containing species at lower potential can transform CO-like poisoning species on Pt to CO₂ in the presence of V₂O₅ which helps in regenerating active sites on Pt for further electrochemical oxidation of methanol. The enhanced electrode response is attributed to synergistic effect between Pt and V₂O₅.