Carbon-coated TiO2 fibers were synthesized as core–shell structured supports for highly dispersed Pt nanoparticles. The catalyst samples were characterized by XRD, Raman, TGA, SEM, TEM and EDX. Performance of methanol oxidation was evaluated in aqueous H2SO4 solutions with methanol by cyclic voltammetry and chronoamperometry. The TiO2 nanofibers were coated with carbon shells mostly between 5 and 10 nm in thickness. Platinum nanoparticles around 2 nm were evenly deposited onto the as-synthesized carbon-coated TiO2 fibers, denoted as Pt–TiO2/C. Electrochemical experiments showed that the peak current density of methanol oxidation in the forward scan was significantly increased by 7.3 and 2.5 times on Pt–TiO2/C compared with those of Pt–TiO2 and Pt–C (Vulcan XC-72), respectively. Furthermore, the Pt–TiO2/C electro-catalyst exhibited a lower onset potential and slower current decay than Pt–C, suggesting higher catalytic activity and better stability. In photo-electrochemical experiments, the electro-catalytic and photo-catalytic properties of Pt–TiO2/C have been synergistically coupled to boost the performance of methanol oxidation. Under UV irradiation, the total peak current density of methanol oxidation on Pt–TiO2/C is enhanced 2.5 times as that in the dark. In brief, the cooperation between Pt, carbon shell and TiO2 support promotes methanol oxidation on Pt–TiO2/C with and without UV illumination.