According to radiation protection theory, the radiation shielding properties of composites are closely related to dispersion condition of radiation absorbing materials in matrix. The more equably radiation-shielding materials dispersed in the matrix, the better the composites' shielding properties are. Rare earth ions have preferably absorbing ability for radiation due to their special electronic structures. From our early work, we know Sm(AA) 3 has good radiationabsorbing ability and excellent compatibility with polymer matrix. Furthermore, Sm (AA) 3 has double key structures which can in-situ react with polymer matrix in vulcanization process. This in-situ reaction can also help Sm(AA) 3 disperse better in the matrix. Based on these, we studied a new method to prepare Sm( AA)3/NR( nature rubber) composites( NR used as matrix), in which Sm(AA)3 dispersed very equably with tiny particle size. Both sulfur and peroxide exist in the system as crosslinking agent. The vulcanization process occurred at the temperature of 110℃ first and a certain degree crosslinking network formed in this stage, which we called pre-vulcanization process in this paper. In this stage sulfur was used as the crosslinking agent. Then continued the vulcanization process at higher temperature(170℃). The peroxide was used as crosslinking agent in this stage. According to reaction-induced phase decomposition mechanism, we studied the phase decomposition changing mode of Sm(AA) 3 in NR matrix of different crosslinking degrees. We also studied the influence of different degrees of pre-vulcanization to the dispersion condition of Sm (AA) 3 in NR matrix. The crystal-fusion status of both Sm(AA) 3 powder and Sm(AA) 3 in cured rubber were observed by DSC (Differential Scanning Calorimetry) and XRD (X-rays Diffraction). The dispersion condition of Sm(AA) 3 in cured rubber was observed by SEM (Scanning Electron Microscopy) and TEM (Transmission Electron Microscope).The studyresults show different degrees of pre-vulcanization have different effect on the in-situ reaction at high temperature (170℃), which influences the dispersion condition of Sm( AA)3 in NR matrix and the composites' final radiationshielding properties directly.