In this paper, the bi-functional properties of NiO-CaO-Al2O3 (Ni-Ca-Al) catalysts derived from hydrotalcite-like precursors were explored for steam reforming of toluene and biomass reactions. The influence of CO2 sorption property of NiO-CaO-Al2O3 catalysts was also explored by changing Ca/Al molar composition ratio for steam reforming reaction. The steam reforming of toluene reaction was investigated at low steam-to-carbon conditions (S/C= 1). An optimum catalyst composition of Ni-Ca-Al(8:62:30) gave superior catalytic performance in terms of stability and activity in both the reforming reactions. At S/C value of I, Ni-Ca-Al(8:62:30) catalyst displayed a stable toluene conversion of near 70% for a period of 24 h tested in toluene reforming reaction. At 650 degrees C, about 85% of biomass was converted to gaseous products over Ni-Ca-Al(8:62:30), which is the highest among all the catalysts tested. The XRD analysis of reduced and spent catalysts shows that the rate of agglomeration of active metallic Ni species over Ni-Ca-Al(8:62:30) catalyst is considerably lesser when compared to other catalysts. The TPR and XPS analyses reveals that the calcined and reduced Ni-Ca-Al catalysts are in Ca(Ni, Al)O solid solution form, respectively. CO2 - TPD studies shows that the basicity of Ni-Ca-Al(8:62:30) catalyst is higher compared to other Ni-Ca-Al catalysts. The rate of carbon deposition over Ni-Ca-A1(8:62:30) catalyst during steam reforming of toluene reaction is 2.5 mgC g(-1) h(-1), which is also the lowest among all the catalysts. Hence, the low carbon deposition rate is one of the reasons for its stable catalytic performance compared to the rest. (C) 2015 Elsevier B.V. All rights reserved.