Newly synthesized nickel calcium aluminum catalysts (Ni/Ca12Al14O33) were tested in a fixed bed reactor for biomass tar steam reforming, toluene as tar destruction model compound. Four catalysts (Ni/Ca12Al14O33) were prepared with Ni loading amount from 1, 3, 5 to 7 wt%, even 1% loading catalyst also showed excellent performance. Catalysts aged experiments in the absence (60 h on stream) and presence of H2S were characterized by BET, X-ray diffraction (XRD), and Raman spectra. It was observed that Ni/Ca12Al14O33 showed excellent sustainability against coke formation due to the "free oxygen" in the catalysts. It also exhibited higher H2S-poisoning resistance property compared to the commercial catalysts Ni/Al2O3 (5%) and Ni/CaO0.5/MgO0.5. Raman spectra revealed that "free oxygen O-2(-) and O-2(2-)" in the structure of the catalysts could be substituted by sulfur then protected Ni poisoning on some degree, but reactivation experiments by 02 flowing showed that the sulfide Ni/Ca12Al14O33 was difficult to completely restore, incorporation of sulfur in the structure only partly regain by O-2. The kinetic model proposes, as generally accepted, a first-order reaction for toluene with activation energy of 82.06 kJ mol(-1) was coincident with the literature data, The Ni/Ca12Al14O33 catalyst was effective and relative cheap, which may be lead to reduction in the cost of hot gas cleaning process. (C) 2008 Elsevier B.V. All rights reserved.