Rhodium nanoislands were spontaneously deposited on Au(111) up to a full coverage. Obtained Rh/Au(111) bimetallic surface was characterized ex situ by Atomic Force Microscopy imaging and by X-Ray Photoelectron Microscopy, while in situ characterization was performed by Cyclic Voltammetry in 0.1 M NaOH solution. Pronounced catalysis of hydrogen evolution reaction has been observed on Rh modified Au(111) surface compared to bare Au(111). This is ascribed to the suitable geometry of obtained Rh/Au(111) nanostructured electrode surface providing large number of active sites and to the electronic interaction between Au(111) substrate and Rh deposit. (C) 2016 The Electrochemical Society. All rights reserved.