The biopolymer Chitosan was used as polymeric precursor for the synthesis of Ni:CeO2 nanocomposite catalysts. Evidences for the formation of a hybrid polymer, of the Cc-citrate complex and the chitosan by polyesterification reaction, was provided by C-13 NMR and Raman spectroscopy. After the heat-treatment of the hybrid polymer at several temperatures, the materials were characterized by N-2 physisorption, H-2 and CO2 chemisorption, XRD, EDX, TEM and Raman analyses. The results show that the presence of residual carbon has a positive influence on the samples properties. It was found that residual carbon contributes to a high surface area and to direct formation of Ni metal during the pyrolysis in N-2 atmosphere. In addition, due to the presence of residual carbon, the catalytic performance in CO2 reforming of CH4 indicated an enhanced stability and coking resistance of the catalysts. (C) 2006 Elsevier B.V. All rights reserved.