Fe2O3/Al2O3 composite at the mass ratio of 3:2 was prepared by sol-gel combustion synthesis using urea as fuel. The optimized preparation parameters were determined by the robust orthogonal experimental design (OED) method. Standard L9(34) orthogonal array was adopted, and the four factors were determined as the molar ratio of oxidizer nitrates to fuel urea Ф, relative amount of the deionized water added Rw, ignition temperature and sintering temperature. Range analysis of the relative importance of those four factors on the mean weight loss rate for the reduction of synthesized Fe2O3/Al2O3 with 50 vol% H2 indicated that the most influential factor was Ф, sintering temperature, Rw and ignition temperature in the descending order. And the optimized preparation parameters for Fe2O3/Al2O3 composite were Ф=1, Rw=7.5, ignition and sintering temperatures stabilized as 600°C and 950°C,respectively. Finally, the reaction characteristics of Fe2O3/Al2O3 prepared by SGCS and the other two reference methods (including sol-gel method and mechanical mixing method) were compared and the results verified that the optimized SGCS was the best option to synthesize Fe2O3/Al2O3 composite with good reaction performance.