The nickel active sites were introduced into TUD-1 mesoporous molecular sieve via grafting, direct synthesis, and impregnation methods. These samples were characterized using powder X-ray diffraction, N2 physisorption, H2 temperature-programmed reduction, H2 chemisorption, TG/DTA, temperature-programmed hydrogenation, Raman spectra and transmission electron microscope to give the insight of physicochemical properties. Catalytic tests probed by the carbon dioxide reforming of methane revealed that Ni-grafted TUD-1 exhibited the highest catalytic activity and long-term stability among these catalysts. Further studies implied catalytic activity, stability and carbon formation were highly sensitive to the metallic nickel particle size which was significantly affected by the introduction method of Ni active sites. Strong anchoring effect inherent to the grafting method was suggested to be the underlying reason for the small Ni particle size and improved catalytic performance.