La2O3 and SrO-doped CaO-MgO-Nb2O5-TiO2 system, ceramics were prepared by solid-state ceramic technique. The microstructure and microwave dielectric properties of CaO-MgO-Nb2O5-TiO2-La2O3 ceramics can be adjusted by varying the amount of La3+ or Sr2+ ions respectively. The replacement of Ca2+ by La3+ at A-site of the ceramics increases the quality factor Q value (at 7.6 GHz) as well as the temperature coefficient of resonant frequency tau(f) and decreases the dielectric constant epsilon(r) and the substitution of Sr2+ at A-site in this ceramics system exhibits opposite characteristics. The microwave properties of La3+, Sr2+-doped CaO-MgO-Nb2O5-TiO2 system ceramics depend on the degree of octahedral distortion, inside materials.