Phases and core-levels of Sm-intercalated C60 thin films are researched with X-ray photoemission spectroscopy. The solid solution phase dominates until the stoichiometry of Sm0.5C60. Below the intercalation level of Sm2.75C60, the sample is phase-separated into the solid solution phase and Sm2.75C60, while the sample is not the mixture of Sm2.75C60 and Sm6C60 with the Sm concentration higher than Sm2.75C60. Experimental data of Sm 4f and 4d clearly reveal the valence state of Sm is divalent for Sm fullerides. Two subpeaks of divalent Sm 3d5/2 level are found.