A Pt/TiO2 nanofiber catalyst has been prepared through the combination of an electrospinning technique with a reductive impregnation method. The compositions, morphologies and structures of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive spectroscopy (EDS). The results showed that the crystal phase of the TiO2 nanofibers was composed of anatase and rutile TiO2. Pt nanoparticles were found to be uniformly distributed on the surface of the TiO2 nanofibers with an average size of 4.0 nm. The mass fraction of Pt in the Pt/TiO2 nanofiber catalyst was about 20%. The electrocatalytic activities of the samples towards the oxidation of methanol were measured by cyclic voltammetry and chronoamperometry using a three-electrode system in an acidic solution. Compared with Pt/P25 and commercial Pt/C catalysts containing the same quality percentage of Pt nanoparticles, the Pt/TiO2 nanofiber catalyst exhibited higher catalytic activity towards the oxidation of methanol and better stability.