To improve the gas production and quality of biomass steam gasification by tar reforming, an iron/olivine catalyst was designed for a use in fluidized bed gasifier. Olivine was impregnated by 1 0 wt% or 20 wt% of iron and calcined at different temperatures (400 degrees C, 900 degrees C, 1000 degrees C, 1100 degrees C or 1400 degrees C). Various characterization techniques such as X-ray diffraction (XRD). Mossbauer spectroscopy, Scanning Electron Microscopy combined with Energy Dispersive X-ray (SEM/EDX), X-ray Photoelectron Spectroscopy (XPS) and Temperature Programmed Reduction (TPR) were performed for detailed physicochemical characterization of Fe/olivine catalyst. Although the iron concentration, calcination temperature is of great importance for establishing interactions between olivine and the added iron. XRD and Mossbauer spectroscopy indicate that iron (II) leaves the olivine structure by oxidation leading to catalysts with high iron (III) contents after calcination between 1000 and 1400 degrees C. The TPR results allow to determine that 10Fe/oliv 1000 degrees C seems to be the best compromise involving significant amount of metallic iron available after reduction and sufficient iron migration through olivine grain. Catalytic reforming of toluene as tar model compound was investigated. Experiments were conducted in a fixed bed reactor at 825 degrees C in the presence of a gas mixture (H-2, CO, CO2 and CH4) representative of the gas present at the biomass steam gasifier outlet. Toluene conversion (91%) and hydrogen production (0.066 mol(H2)/h/g(cat)) were three times higher than with olivine (39% of conversion and 0.010 mol(H2)/h/g(cat) of H-2 production). Characterizations performed after tests indicate that a high percentage of iron in its metallic form is maintained leading to C-C and C-H bonds break and a sufficient percentage of iron (II) is available by simple oxidation in the olivine structure. Carbon formed by toluene decomposition is oxidized due to the presence of high water concentration. These observations can explain the efficiency and stability of the Fe/olivine catalyst. This work illustrates that 10Fe/oliv 1000 degrees C, which is a non toxic and cheap catalyst, has properties for tar steam reforming and for a use in biomass steam gasification in a fluidized bed. (C) 2010 Elsevier B.V. All rights reserved.