Metal oxides-modified Ni-based catalysts for glycerol steam reforming (GSR) to syngas were prepared by impregnation using commercial Ca-containing Linde-type 5A zeolite (LTA) as support, and characterized by XRD, N2-adsorption, CO2-TPD, H2-TPR, and TPO. The XRD and CO2-TPD results indicated that the introduction of alkali and rare earth metals could modify the basic property of Ni/LTA catalysts. H2-TPR results indicated that the simultaneous presence of Mo–La oxides and nonskeletal CaO in Ni/LTA weakened the strong interaction between Ni active metal species and support (SIMS). The catalytic test showed that increase on basic property of Ni/LTA catalysts was helpful to improving glycerol conversion to syngas and inhibiting water–gas shift reaction and methanation during GSR. The Ni/MoLaCa-LTA with a weakened SIMS gave rise to the formation of smaller NiO particles, and exhibited a stable production capacity of gas with a H2/CO ratio of around 2.17, and exhibited no deactivation during 100h time-on-stream. Although Ni/MoZrCa-LTA in GSR was rapidly deactivated due to carbon deposit after running 40h, the spent catalyst could be on-line regenerated by calcination at 700°C in an air flow, which could also be proved by TPO results of spent catalysts.