Carbon supported Pt and Au nanoparticles with small sizes (2.4 nm for Pt/C, and 3.5 nm for Au/C) and narrow size distributions were prepared though a modified solution-phase reduction method, and served as the working catalysts for an investigation of electrocatalytic oxidation of EG in alkaline media. Our three-electrode cell with an on-line sample collection system showed that with applied potential increasing, glycolic acid, oxalic acid and formic acid were sequentially produced from EG oxidation on Pt/C, while only glycolic acid and formic acid were detected on Au/C. Oxalic acid is a fairly stable product, and Pt/C is inactive to its further oxidation reaction. On Au/C, glycolic acid is the primary product, and no oxalic acid was found at specified test conditions. We clarified that formic acid was produced preferably from direct C C bond cleavage of EG not glycolic acid on both Pt/C and Au/C catalysts. The single anion exchange membrane-direct EG fuel cell (AEM-DEGFC) with Pt/C and Au/C anode catalysts showed consistent results with the three-electrode cell tests. The AEM-DEGC with Pt/C anode catalyst demonstrated a peak power density of 71.0 mW cm(-2), which is much higher than that with the Au/C (only 7.3 mW cm(-2)) at 50 degrees C. With the fuel cell operation voltage decreasing (anode overpotential increasing), deeper-oxidized products oxalic acid and formic acid were generated in the Pt/C anode AEM-DEGFC with higher selectivity. No formic acid was detected in the Pt anode AEM-DEGFC when glycolic acid was employed as fuel. On Au/C anode catalyst, very high selectivity to glycolic acid (>98%) was achieved. The AEM-DEGFC results confirmed the EG electro-oxidation pathways proposed by using an on-line sample collection system. (C) 2012 Elsevier B.V. All rights reserved.