New low‐temperature sinterable dielectric materials based on Li2CaSiO4 (LCS) ceramic has been developed. The LCS ceramics were prepared by solid‐state ceramic route. The calcination and sintering temperatures of LCS were optimized as 800°C/4 h and 1000°C/2 h, respectively, for the best density and dielectric properties. The dielectric properties of the ceramic were measured in the radio frequency by parallel plate capacitor method and in the microwave frequency range by cavity perturbation technique. The LCS sintered at 1000°C/2 h had ɛr=4.36 and tan δ=0.003 at 8 GHz. The sintering temperature of LCS is lowered from 1000°C to 850°C/2 h for low‐temperature co‐fired ceramic application by the addition of different borosilicate glasses with reasonably good microwave dielectric properties. The stability of the glass–ceramic composites with temperature was also investigated.