Fluorescence material of Sm doped Si-Ca-Mg system was synthesized by using the method of solid phase reaction at high temperature. The phase composition and crystal structure of this material were analyzed with XRD method for its composition and the existence form of Sm atom. We aimed to exactly determine the phase composition of this fluorescence material and the doping position and environment of rare-earth Sm atom in the system because these factors have significant effects on the properties. The analytical results show that the Sm atoms dope in Ca2O26Si6Sm8 lattice in the form of atomic site-occupation in three different space positions with different occupancy rates. Therefore, based on the XRD analytical results, the fluorescence material of Sm doped Si-Ca-Mg system with high performance can be synthesized.