CaO doped iron-alumina-supported nickel-iron alloy catalysts were tested in a fixed-bed reactor for steam reforming of toluene as a biomass tar model compound at a relatively low steam-to-carbon (S/C) ratio of 2. The influence of doping CaO to iron-alumina support was also explored for the steam reforming reaction. Ni supported on a CaO(1.5)-Fe2O3-Al2O3 support (Ni/Ca(1.5)-Fe-Al) gave superior catalytic performance in terms of activity and stability over other catalysts. Ni/Ca(1.5)-Fe-Al gave a toluene conversion of more than 80% for a period of 22 h testing at a S/C ratio of 2. XRD analysis showed that the Ni-Fe alloys formed were stable throughout the reforming reaction. It was observed from XPS results that the surface of the reduced Ni/Ca(1.5)-Fe-Al catalyst was enriched with Fe species compared to other catalysts. These enriched surface Fe species play the role of co-catalysts by increasing the coverage of oxygen species during the reforming reaction to enhance the reaction of toluene and to suppress coke formation. The temperature-programmed surface reaction (TPSR) with water reveals that the Ni/Ca(1.5)-Fe-Al catalyst can activate water molecule at relatively lower temperature over other CaO doped catalysts. TGA analysis on spent catalysts reveals that all CaO-containing catalysts generally result in lower carbon formation rates as compared to Ni/Fe-Al catalyst. (C) 2014 Elsevier B.V. All rights reserved.