Zn K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the structure of Zn monolayers prepared on Au(1 1 1) electrodes via underpotennal deposition (UPD) from phosphate supporting electrolyte Theoretical modeling of the XAS data indicates that the Zn adatoms adopt a commensurate (root 3 x root 3)R30 degrees (theta(sc) = 0 33) adlayer structure and reside within the 3-fold hollow sites of the Au(1 1 1) surface Meanwhile phosphate counter-ions co-adsorb on the UPD adlayer and bridge between the Zn adatoms in a (root 3 x root 3)R30 (theta(sc) = 0 33) configuration with each phosphorous atom residing above a vacant 3-fold hollow site of the Au(1 1 1) Significantly this surface structure is invariant between the electrochemical potential for UPD adlayer formation and the onset of bulk Zn electrodeposition Analysis of the Zn K-edge absorption onset also presents the possibility that the Zn adatoms do not fully discharge during the process of UPD which had been proposed in prior voltammetnc studies of the phosphate/Zn(UPD)/Au(1 1 1) system (C) 2010 Elsevier Ltd All rights reserved