A Fe-based oxygen carrier (OC) was evaluated for H-2 production with CO2 capture by coupling steam reforming of methane and chemical-looping combustion (CLC) processes (SR-CLC). The CLC system supplies the heat necessary to carry out the endothermic reformed reactions, using the PSA off-gas as fuel. The Fe-based OC was made by incipient hot impregnation using Al2O3 as support and was first characterized by TGA and batch fluidized bed reactor in order to determine its reactivity and its fluidization behavior. The OC behavior in a continuous CLC unit was evaluated using a simulated PSA off-gas and methane as fuels. During 46 h of continuous operation, the OC never showed agglomeration or carbon deposition, and the attrition was moderate. It was found that the fuel composition has low effect on the combustion efficiency and full conversion can be obtained at 1153K with an oxygen carrier-to-fuel ratio> 1.5. The solids inventory needed to fully convert methane or PSA off-gas was lower than those found with other Fe-based materials. These results were due to the positive effect of the alumina on the OC reactivity. Therefore, the Fe2O3/Al2O3 OC prepared by impregnation is suitable for burning a PSA off-gas in the SR-CLC process. (C) 2011 Elsevier B.V. All rights reserved.