Ca1-x(Li1/2Sm1/2)xTiO3 microwave dielectric ceramics in the x range of 0.70 ~ 0.80 were prepared by conventional ceramics fabrication technique. The crystal structure, microstructure and microwave dielectric properties were investigated. The results showed that a single orthorhombic perovskite structure formed within this x range, and the substitution of (Li1/2Sm1/2)2+ ion for Ca2+ ion in A-site has a significant influence on the microwave dielectric properties of the ceramics. With the increase of substitution of (Li1/2Sm1/2)2+ ion with 0.75, the temperature coefficient of resonant frequency τf reaches zero, and it could be attributed that the Sm and Li have a polarizability effect according to its microstructure. The Ca0.25(Li1/2Sm1/2)0.75TiO3 ceramic had a good performance with microwave dielectric properties of τf = 0 ppm/°C, εr = 105.83, and Qf = 3170 GHz.