Ag and AgNi powders were comparatively tested as anodic catalysts for direct electrochemical oxidation of borohydride. Discharge experiments demonstrated for the first time that both Ag and AgNi electrode can catalyze the electrooxidation of borohydride, delivering a high capacity of > 7e oxidation for a borohydride ion. In comparison, AgNi-catalyzed borohydride fuel cells exhibited a higher discharge voltage and capacity, possibly due to a combined action of the electrocatalytic activity of Ni component for borohydride electrooxidation and the depression of borohydride hydrolysis by Ag atoms. (C) 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.