Ni/Al2O3 catalysts modified with metal oxides for biomass glycerol steam reforming to syngas were prepared by impregnation, and also characterized by XRD, H-2-TPR and NH3-TPD technologies. In order to produce more methanol syngas (H-2/CO = 2), methane was introduced into biomass glycerol reforming system. The results indicated that Ni/Al2O3 with support modification by Ca-Mg oxides and catalytic active phase adulteration by La-Ce-Zr oxides exhibited an excellent catalytic performance for a high production of syngas. Both CO2 ( < 2.8%) and methane (about 0.07%) contents were very low in the obtained reforming gas with a (H-2 -CO2 )/(CO + CO2) molar ratio of about 2.09, which fitted the feedstock demand for the conventional methanol industry. It was also found that the main function of introduced methane in glycerol steam reforming system was to inhibit CO2 production through the dry reforming. Under the optimized conditions, methanol syngas yield reaches up to about 87.7% based on glycerol conversion, much higher than that in glycerol steam reforming without methane.