The present work aims to investigate the steam reforming (SR) of liquid hydrocarbons toward hydrogen production, employing iso-octane as gasoline surrogate, over Cu catalysts supported on rare earth oxides (REOs). An extensive characterization study, involving Xray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and temperature-programmed reduction (TPR), is undertaken to correlate the structural, morphological and surface properties of catalysts with their reforming performance. Several parameters related to the effect of operation temperature (600 - 800 degrees C), steam/carbon ratio (1-3) and Cu loading (0-25 wt%) on the catalytic performance are investigated. The results reveal that the best performance is obtained over the Cu/CeO2 catalysts at a steam/carbon ratio of 3; H-2 yields as high as similar to 55% are obtained at the expense of CH4 and higher hydrocarbons. Concerning the influence of oxide carries on reforming efficiency the following order, in terms of H-2 yield, is recorded: CeO2 >> Nd2O3 > Gd2O3 > Sm2O3 approximate to Pr6O11 approximate to La2O3. However, a notable deterioration of Cu/CeO2 catalyst is observed in long term stability tests, ascribed to carbon deposition and catalyst sintering. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.