Hydrogen production from the pyrolysis/reforming of refuse derived fuel (RDF) was investigated with a series of Ni/SiO2 catalysts. The catalysts were prepared by homogeneous precipitation derived from a sol-gel method (HPG) and compared to Ni/SiO2 catalysts prepared by adding a phase separation step to the HPG process (B-HPG). All the catalysts had a NiO loading of 10 wt.%, and three different calcination temperatures (500 degrees C, 700 degrees C and 900 degrees C) were used for each method. The prepared Ni/SiO2 catalysts were analysed to determine their surface area, and porosity characteristics; additionally scanning electron microscopy (SEM-EDX), transmission electron microscopy (TEM), infrared spectroscopy (FTIR), and X-Ray diffraction (XRD) analyses were carried out. The results showed that the catalyst prepared by HPG and calcined at 700 degrees C (HPG700), presented a relatively high surface area (similar to 347 m(2) g(-1)), large pore diameter (12.50 nm), and also resulted in the highest catalytic activity towards H-2 production, attaining similar to 60 vol.% hydrogen. The lowest hydrogen concentration of about 42 vol.% was obtained using the catalysts prepared by the combined HPG-phase separation method, and calcined at 900 degrees C (B-HPG900). It was also observed that at calcination temperatures higher than 700 degrees C the catalytic activity for hydrogen production was diminished for both preparation methods. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.