A Ni-B amorphous alloy catalyst (AP Ni) was prepared and used in an aqueous-phase reforming (APR) of glycerol. Higher stability and higher selectivity towards H-2 were obtained when compared with Raney Ni. After 130 h' on stream aqueous-phase reforming of glycerol, the amorphous Ni-B catalyst was transformed to hexagonal closed-packed (hcp) Ni crystallites. The high selectivity towards hydrogen and catalytic stability may be due to the formation of hcp Ni crystallites during reaction and the protection of B2O3. The AP Ni catalyst was found to be 35-50% more active in terms of the H-2 production rate and 17-31% more selective toward H-2 as compared to Raney Ni. The reforming reaction at different reaction temperature, feedstock concentration, feedstock flow rate and other biomass derivatives i.e., ethylene glycol and sorbitol, were also investigated over AP Ni catalyst. Crown Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.