Steam reforming of two representative components in the aqueous fraction of bio-oil, acetone and ethanol, was investigated over nickel based supported catalysts (Ni/Al2O3). The effect of Rh incorporation (Ni-Rh/Al2O3) and the properties of different gamma-Al2O3 used as support was tested. Hydrogen-rich gas is produced at temperatures higher than 673 K in both acetone and ethanol reforming with maximum mole fraction of 0.6-0.7. The reactions involved and the possible routes were studied. Rh incorporation and nanostructured alumina affects the Ni metal size and the amount of carbon deposited onto catalysts' surface after reforming tests; besides, acetone is also found as an important intermediate in ethanol reforming, and Rh improve hydrogen production with negligible intermediates presence. The effect of S/Acetone or S/Ethanol feed molar ratios, space velocity and temperature over acetone/ethanol conversion and over H-2/CO ratio were modeled using the Matlab software in order to find the regions and the optimal operating conditions in both processes. Simulation results are consistent with the experimental data. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.