Direct ethanol fuel cells (DEFCs) offer an attractive alternative to fossil fuel-powered devices due to their high energy density and environmental benignity. However, high cost and poor stability of catalysts are still the main obstacles for the commercialization of DEFCs. Herein, a novel catalyst comprising PtRh alloys anchored on carbon nanotubes that decorated with tungsten nitride (Pt9Rh-WN/CNTs) was synthesized via impregnation reduction method and followed by thermal annealing in N-2. The X-ray powder diffraction (XRD), scanning electron micrograph (SEM) and transmission electron microscopy (TEM) are employed to characterize the corresponding physico-chemical properties of the as-prepared catalysts. Electrocatalytic performance for ethanol oxidation is evaluated by cyclic voltammetry, linear scan voltammetry, CO-stripping voltammograms, chronoamperometry and chronopotentiometry. The current density on Pt9Rh-WN/CNTs is 484.8 mA mg(Pt)(-1), which is much higher than that of Pt9Rh/CNTs (305.7 mA mg(Pt)(-1)) and Pt/CNTs (135.1 mA mg(Pt)(-1)). Most importantly, the onset potential for CO oxidation on Pt9RhWN/CNTs is 0.27 V, which is more negative than that on Pt9Rh/CNTs (0.37 V) and Pt/CNTs (0.40 V). Therefore, the Pt9Rh-WN/CNTs catalyst displays both outstanding catalytic activity and excellent CO-poisoning tolerance for ethanol oxidation. Synergistic effects arising between WN and PtRh alloy along with nitrogen-doping effects of CNTs with ammonia are proposed to contribute to the outstanding performance of this catalyst in ethanol oxidation. (C) 2017 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.