A novel catalyst, Pt-PMo 12 -CNT, with well-dispersed Pt nanoparticles and monolayer PMo 12 on multi-walled carbon nanotubes (CNTs) is reported. A polyoxometallate (PMo 12 ) 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 PMo 12 monolayers. The as-prepared Pt-PMo 12 -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 12 -CNT catalysts are discussed.