In this work we study the electrochemical growth and dissolution of a Ni on Pd-Au(1 1 1) bimetallic surfaces using in situ scanning tunnelling microscopy We also compare Ni deposition on monometallic electrodes le Au(1 1 1)and Pd(1ML)/Au(1 1 1) usingelectrochemical characterizations Results evidence that the first Ni monolayer grows preferentially on Au(1 1 1) in a wide potential range and that a full Ni monolayer covering the entire Pd-Au surface can be selectively dissolved from Pd Islands No such selectivity is observed upon growth of subsequent Ni atomic planes We demonstrate that the Ni-substrate interactions play a key role in the above mentioned selectivity The binding energy of Ni to Pd is found to be 80 meV smaller than of Ni to Au The sign and the amplitude of this difference are discussed in light of the d band filling of the Pd-Au(1 1 1) bimetallic surface and the presence of adsorbed H on Pd before deposition (C) 2010 Elsevier Ltd All rights reserved