Sm1.9Ca0.1Zr2O6.95 ceramic was sintered at 1600°C for 10 h in air by solid-state reaction method. The phase structure and thermal expansion coefficient were measured by XRD and a high-temperature dilatometry, respectively. The results show that the crystal structure of Sm1.9Ca0.1Zr2O6.95 ceramic is still pyrochlore. The doping with calcium cation leads to a shift of the X-ray spectrum of Sm1.9Ca0.1Zr2O6.95 ceramic to lower 2θ values. The experiments also show that the thermal expansion coefficients of Sm1.9Ca0.1Zr2O6.95 ceramic are higher than those of Sm2Zr2O7 ceramic. These results are related to the vacancy induced by doped calcium cation in the samarium lattice.