Monodispersed Pt nanoparticles supported on a TiO2 and nitrogen-doped carbon composite (TiO2/NDC) were successfully synthesized via an efficient in situ self-assembly strategy and microwave-assisted polyol process. The Pt/TiO2/NDC catalyst exhibited superior electrocatalytic activity toward the methanol oxidation reaction (MOR). The electrochemically active surface area of the Pt/TiO2/NDC catalyst was twofold higher than that of the Pt/C/NDC catalyst. In addition, the Pt/TiO2/NDC catalyst revealed a better electrocatalytic activity and CO-tolerance as well as a stability toward the MOR. The combined characterization from Fourier transform infrared spectrum, Brunauer-Emmett-Teller surface area, scanning electron microscopy, transmission electron microscopy, energy dispersive spectrometer, thermogravimetric analysis, inductively coupled plasma atomic emissions spectrometry, X-ray diffraction, and X-ray photoelectron spectroscopy analyses demonstrated that the superior catalytic performance and stability of the Pt/TiO2/NDC catalysts likely arose from the synergistic effect of their unique morphology and composition as well as the electronic effect between the TiO2/NDC and Pt. This electrocatalyst holds great promise for application in direct methanol fuel cells.