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A ternary Sm(Ⅲ) complex with salicylate (sal-) and o-phenanthroline (phen) was synthesized and incorporated in silica matrix by sol-gel method. The luminescence behavior of the complex in silica gel was studied compared with that of the pure complex by means of emission, excitation spectra and thermogravimetic analysis. The results indicate that the fluorescence intensity ratio of the 4G5/2→6H9/2 transition to the 4G5/2→6H5/2 transition in silica gel doped with Sm(sal)3(phen) is lower than that of the pure Sm(sal)3(phen). The thermal stability of Sm(sal)3(phen) is enhanced greatly by the introduction of the complex into silica matrix. An isolated and chemical inert environment of the complex appears to be responsible for the thermal stability enhancement in silica gel.