A novel catalyst, Pt-PMO]2-CNT, with well-dispersed Pt nanoparticles and monolayer PM012 on multiwalled carbon nanotubes (CNTs) is reported. A polyoxometal late (PM012) was chemically adsorbed on the surface of Pt nanoparticles and on outer walls of CNTs. These effectively prevented the agglomeration of Pt nanoparticles and CNTs due to the electrostatic repulsive interactions between negatively charged PM012 monolayers. The as-prepared Pt-PM012-CNT materials show higher electrocatalytic activity, higher cycle stability, and better tolerance to poisoning species in methanol oxidation than do Pt-CNT catalysts prepared by the same method. The reasons for the improved catalytic performance of the Pt-PMO,2-CNT catalysts are discussed.