In the present work, core-shell Ni@SiO2 catalysts were investigated in order to evaluate the relevance of catalytic activity and surface states of Ni core as well as Ni nanoparticles size to catalytic partial oxidation of methane (POM). The catalysts were characterized by N2 adsorption, H2-TPR, XRD, TEM and XPS techniques. The catalytic performance of the core-shell catalysts was found to be dependent on the surface states of catalyst, which influenced the formation of products. It was considered that carbon dioxide formed on the oxidized nickel sites (NiO) and carbon monoxide produced on the reduced sites (Ni). The surface states of active metal in the dynamic were influenced both by the size of Ni core and the porosity of silica shell. However, the catalytic activity would be debased when the size of Ni core was under a certain extent, which can be ascribed to the fact the carbon deposition increased with the increasing content of NiO. The effects of surface states of Ni@SiO2 catalyst on the catalytic performance were discussed and the reaction pathway over Ni core encapsulated inside silica shell was proposed.