Low-temperature sintered Ca[(Li1/3Nb2/3)0.8Ti0.2]O3-δ (CLNT) microwave dielectric ceramics with V2O5 and ZnO additives were prepared by the conventional solid state reaction method. The sintering behavior and microwave dielectric properties of CLNT ceramics were investigated. The main diffraction peaks of all the specimens sintered at the temperature under 1150◦C split due to the coexistence of the non-stoichiometric phase and stoichiometric phase, which all possess CaTiO3-type perovskite structures. ZnO and V2O5 combined additives lowered the sintering temperature of CLNT ceramics from 1150◦C to 1090◦C. and the Qf values were improved from 18,210 GHz to 20,740 GHz. The CLNT ceramics with 4 wt% ZnO addition sintered at 1090◦C showed good microwave dielectric properties with εr ~39.7, Qf ~20,740 GHz, τf ~8.6 ppm/◦C. The relationship between dielectric properties and the sintering behavior was also discussed.