An Au/C catalyst was prepared by means of the polyvinyl alcohol-protected Au sol method. Highly dispersed Au nanoparticles with an average particle size of around 3.7 nm were obtained as confirmed by transmission electron microscopy. The cyclic voltammogram of Au/C was similar to that of a bulk Au electrode, but a small shift of Au oxide reduction and oxidation potential peaks were observed. The electrooxidation of methanol, ethanol, ethylene glycol, and glycerol on the Au/C catalyst in an alkaline solution was analyzed. Using a cyclic voltammogram, the maximum current density toward alcohol electrooxidation was found to decrease in the order of glycerol > ethylene glycol > ethanol, while methanol was not oxidized. Compared with PtRu/C, the maximum current densities obtained from the Au/C catalyst for ethylene glycol and glycerol electrooxidation were increased by 1.6 and 3.3 times, respectively. The reaction heavily progressed through a C-C bond dissociation path. It was found that main product of glycerol electrooxidation was formic acid, which accounted for more than 60 % of the total product. Using chronoamperometry, the Au/C catalyst showed much better stability than that of PtRu/C for the reaction without C-C bond dissociation and better stability for the reaction with C-C bond dissociation.