Improving the electrocatalytic activity, durability, and utilization of anode eletrocatalysts are crucial for accelerating commercialization of direct formic acid fuel cells. In this work, the multiwall carbon nanotubes (MWCNTs) supported PtAu alloy nanocrystals (MWCNTs/PtAu) composites are synthesized by a one-pot wet-chemical method using polyethyleneimine as the complexant and surfactant. The physicochemical properties of the as-prepared MWCNTs/PtAu composites are characterized detailedly by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy, etc. These structural investigations display the PtAu alloy nanocrystals are highly dispersed on the surface of the MWCNTs. Cyclic voltammetry and chronoamperometry measurements show the as-prepared MWCNTs/PtAu composites significantly enhance the direct dehydrogenation pathway of the formic acid oxidation reaction, resulting in the improved electocatalytic activity and durability for the formic acid electrooxidation. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.