Novel glass–free low temperature firing microwave dielectric ceramics Li 2 CeO 3 with high Q prepared through a conventional solid‐state reaction method had been investigated. All the specimens in this paper have sintering temperature lower than 750°C. XRD studies revealed single cubic phase. The microwave dielectric properties were correlated with the sintering conditions. At 720°C/4 h, Li 2 CeO 3 ceramics possessed the excellent microwave dielectric properties of ε r = 15.8, Q × f = 143 700 (GHz), and τ f = −123 ppm/°C. Li 2 CeO 3 ceramics could be excellent candidates for glass‐free low‐temperature co‐fired ceramics substrates.