A systematic investigation was conducted of the surface properties and the HER at electrodes of nominal composition Ti/RhxTi((1-x))O-y prepared by thermal decomposition (T-cal: 500 degrees C; t(cal): 2h; O-2 flux: 5 dm(-1) min(-1)) from salt precursor solutions dissolved in 6.0 mol dm(-3) HNO3. Films were characterized ex situ by SEM, EDX, XPS and XRD and in situ by open circuit potential measurements and CV. The electrochemical behaviour was investigated by CV as function of the anodic, E-lambda,E-a, and cathodic, E-lambda,E-c, switching potentials showing the Rh surface oxidation states strongly depend on these experimental variables. Surface Rh-sites are reduced to metallic rhodium in the cathodic potential region while higher oxidation states (I-III) are formed at more positive potentials (E >= 0.5 V/RHE). Hydrogen adsorption and desorption peaks as well as a short double layer charging region are observed at intermediate potential values. The HER was investigated by Tafel coefficients and reaction order with respect to H+ as function of nominal Rh-content. (c) 2006 Elsevier Ltd. All rights reserved.