A new and simple method to prepare Al2O3 and NiAl2O3 spherical catalysts for hydrogen production by steam reforming of ethanol is proposed. The present method was developed using a biopolymer (chitosan) and Al solution. A hybrid spherical compound of aluminum hydroxide and the biopolymer is formed. Through polymer elimination by thermal treatment, porous spheres with a high specific surface area and large pore volume are obtained. The Ni/Al2O3 spheres showed a high catalytic activity in ethanol steam reforming and hydrogen selectivity at temperatures between 450 and 650 degrees C. In all cases no CO was detected indicating that the Ni/Al2O3 spheres could be considered as a good choice for hydrogen production from ethanol steam reforming for fuel-cell applications. (c) 2006 Elsevier B.V. All rights reserved.