To address the issues of catalytic activity and stability of the promising Fe₂O₃/SiO₂ catalyst for sulfuric acid decomposition, Fe₂O₃ was immobilized on SiO₂ support by polyol, solvothermal and wet-impregnation methods and examined. The different methods yielded catalysts with varying crystal structure, porosity, morphology and redox properties which were investigated by XRD, Mössbauer spectroscopy, N₂-BET surface area, SAXS, ED-XRF, HR-TEM, TPR/O and XPS techniques. The effect of the properties on the activity and stability was evaluated in a fixed-bed reactor and a structure-activity correlation was established. Above 750 ^oC the catalytic activity followed the order polyol > wet impregnation ~ solvothermal. Stability of the sample prepared by polyol method was ascertained by 100 h experimental run at 800 ^oC. The higher activity and stability of the Fe₂O₃/SiO₂ catalyst (polyol) is ascribed to the development of crystalline α-Fe₂O₃ dispersed phase, higher pore confinement, better support-active phase interactions and higher degree of reduction.