We report a facile approach to prepare high density of tiny Pt nanoparticles less than 3 nm loaded on the polyaniline hollow tubes in uniform way. Polyaniline hollow tubes in diameter of micro size are synthesized via the polymerization of aniline onto the template of sulfonated electrospun polystyrene fibers, followed by the removal of core polystyrene fibers. The as-prepared highly crystalline Pt nanoparticles on the surface of polyaniline microtubes show the much higher electrochemical active surface area of 90.49m(2)/g, high mass catalytic current density, good durability toward the methanol oxidation reaction as well as the excellent carbon monoxide tolerance. The hollow-structure-conductive-polymer-based synthesis strategy for high performance catalyst in this study could be applied to produce other catalysts with the enhanced activities.