Production of syngas from lignocellulosic biomass though pyrolysis is a promising solution for the large-scale utilization of biomass. However, current pyrolysis approaches suffer from the relative low product yield and selectivity, limiting their practical application. To solve this problem, a series of nickel-based catalysts including Ni/MCM-41, Ni-5CeO2/MCM-41, and Ni-5La2O3/MCM-41 were prepared and characterized by transmission electron microscopy (TEM), N2 adsorption–desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and H2-temperature-programmed reaction (TPR) analysis. It was observed that the simultaneous addition of Ni and CeO2 to MCM-41 could increase the reducibility of Ni and the number of active Ni0 sites on the surface of the catalyst. Consequently, Ni-5CeO2/MCM-41 gave a CH4 yield of 14.6 mmol/g, which is remarkably higher than that (10.5 mmol/g) obtained in the absence of the catalyst. Meanwhile, the CO and H2 yields increased slightly, while the CO2 yield decreased slightly. Therefore, the improved CH4 yield and selectivity was mainly due to the increased decomposition of tarry compounds catalyzed by Ni/MCM-41 with the assistance of CeO2.