The increasing attention addressed toward the synergic effect of various metals on the catalysis of one of the most important electrocatalytic reaction, such as the Oxygen Reduction Reaction (ORR), led us to study the effect of monolayers of Fe and of mixed Fe and Co on Ag(111), whose catalytic activity is already known and well characterized. Fe and Co/Fe clusters were obtained by the Selective Electrodesorption Based Atomic Layer Deposition (SEBALD) method, which is a novel electrochemical route to deposit metal clusters on a foreign substrate recently proposed by our group. SEBALD of Fe or Co/Fe resulted in an enhanced catalytic activity; Co/Fe in particular was demonstrated to assemble in small clusters, providing access of the electrolyte to Ag and enabling a bimetallic catalytic effect. (C) 2013 Elsevier B.V. All rights reserved.