The composite of polyphosphazene-coated carbon nanotubes is prepared by a simple and efficient synthesis method and regarded as an improved catalyst support for direct methanol fuel cell. Catalyst of Pt-Co supported on polyphosphazene-coated carbon nanotubes is prepared using mixed reducing agents. The PZAF/MWCNTs, PZS/MWCNTs, Pt-Co/PZAF-MWCNTs and Pt-Co/PZS-MWCNTs are measured by transmission electron microscopy. X-ray diffraction and inductively coupled plasma. The electrocatalytic activity of Pt-Co/PZAF-MWCNTs, Pt-Co/PZS-MWCNTs catalysts for methanol oxidation has been investigated by cyclic voltammetry. The composite of Pt-Co/PZAF-MWCNTs shows a good distribution, small particle size and high mass activity. (C) 2012 Elsevier B.V. All rights reserved.