Catalytic materials containing aluminum and iron oxide were synthesized through the preparation of hybrid spheres containing Fe and M hydroxides and an organic polymer (chitosan). The materials were characterized by TGA, DSC, FTIR, ICP-OES, N-2 adsorption/desorption isotherms, XRD, TPR-H-2 and SEM. Regularity in the diameter of the spheres as well as high surface area and pore volume was observed. Catalytic tests showed that the samples were active in the dehydrogenation of ethylbenzene in the presence Of CO2 with good styrene selectivity. The synthetic method of catalysts described here makes possible the in situ formation of the FeAl2O4 phase, which is important for the ethylbenzene dehydrogenation reaction. (C) 2009 Elsevier B.V. All rights reserved.