C-C bond cleavage during electrocatalytic oxidation of glycerol and C3+ polyols often occurs and can significantly affect the Faradaic efficiency, fuel utilization, and output power density of a direct polyol fuel cell, although this has not been deeply investigated. With the goal of acquiring new knowledge of C-C bond breaking of polyols, this study examines the electrocatalytic oxidation of a C-4 polyol mesoerythritol on carbon nanotube supported Pd-based catalysts (Pd/CNT, PdAg/CNT, and PdAg3/CNT) in an anion-exchange membrane fuel cell (AEMFC). Our results show that PdAg/CNT improves the fuel efficiency of meso-erythritol oxidation by contributing to the C-C bond cleavage of meso-erythritol in C3 and C2 chemicals. Based on the analysis of electro-oxidation products and half-cell cyclic voltammetry (CV) of intermediates, a meso-erythritol electro-oxidation pathway has been proposed to demonstrate that Ag is likely to assist Pd to promote the cleavage of C-C bonds of meso-erythritol. (C) 2017 Elsevier B.V. All rights reserved.