To achieve the practical application of direct methanol fuel cells, it is highly important to develop effective electrocatalyst with high activity and favorable durability. Herein, we report the successful preparation of PtCu bimetallic nanoparticles supported on ceria/multi-walled carbon nanotubes composite (PtCu-CeO2/MWCNTs) via microwave-assisted polyol reduction procedure. The composition and morphology of as-obtained composite catalysts were characterized by X-ray diffraction, Raman, X-ray photoelectron spectra, scanning electron microscopy and transmission electron microscopy. The synergistic effects combining PtCu bimetallic effect and oxygen vacancy effect in ceria of such composite catalysts provide abundant active surface area and enhanced conductivity for the effective charge transport during the methanol oxidation reaction (MOR) process. As a results, the PtCu-CeO2/MWCNTs with optimized Pt proportion achieve greatly enhanced MOR activity with mass activity of 1.28 A mg(-l)pt and specific activity of 2.03 mA cm(-2) , superior CO tolerance and reliable stability in contrast to that of commercial Pt/C catalysts. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.