Newer catalysts for the methane reforming with H2S are designed, which are based on Fe2O3/gamma-Al2O3, nanocrystalline gamma-Al2O3 supports, and 1.0 to 6.0 wt% Fe. The main phases are identified as hematite and gamma-Al2O3, with sizes of about 2-4 nm. The structural features are characterized by X-ray diffraction, Rietveld's Refinement and Radial Distribution Function analysis. The textural properties of these catalysts are determined by N-2 sorption and surface fractal dimension calculations. Also, the electronic states are inferred by Mossbauer and UV-Vis (diffuse reflectance) spectroscopies. The activity of Fe2O3/gamma-Al2O3 catalysts in the methane reforming is tested in a fixed bed type reactor. Further calculations indicate that Fe2O3/gamma-Al2O3 catalysts go through a charge transfer decrease, which depends on the iron content, i.e., from 1.08 to 0.88 eV; Mossbauer spectroscopy reveals that Fe3+ ions adopt a tetrahedral coordination, which coincides with their higher activity for hydrogen production, with respect to catalysts having octahedral coordination. The specific surface area of these catalysts is about 84 m(2) g(-1), with a mean pore diameter of 2.5 nm. A mechanism for the methane reforming with H2S is proposed herein. (C) 2015 Elsevier B.V. All rights reserved.