The Pt nanoparticles have been well dispersed on electrospinning-derived carbon fibrous mats (CFMs) by using formaldehyde vapor as reducer to react with H2PtCl6·6H2O adsorbed on the CFMs at 160°C. The prepared electrodes of Pt-CFMs have been characterized by using scanning electron microscopy, transmission electron microscopy and X-ray diffraction spectroscopy, and the performance of the electrodes for methanol oxidation has been investigated by using cyclic voltammetry, chronoamperometry, quasi-steady state polarization and electrochemical impedance spectroscopy techniques. The results demonstrate that Pt-CFMs electrodes exhibit peak current density of 445mAmg−1 Pt, exchange current of 235.7μAcm−2, charge transfer resistance of 16.1Ωcm2 and better stability during the process of methanol oxidation, which are superior to the peak current density of 194mAmg−1 Pt, exchange current of 174.7μAcm−2 and charge transfer resistance of 39.4Ωcm2 obtained for commercial Pt/C supported on CFMs. It indicates that the novel process in which formaldehyde vapor is used as reducer to prepare Pt catalyst with high performance can be developed.