The effects of V2O5 addition on the sintering behavior, microstructure, and the microwave dielectric properties of 5Li2O–0.583Nb2O5–3.248TiO2 (LNT) ceramics have been investigated. With addition of low‐level doping of V2O5 (≤2 wt%), the sintering temperature of the LNT ceramics could be lowered down to around 920°C due to the liquid phase effect. A secondary phase was observed at the level of 2 wt% V2O5 addition. The addition of V2O5 does not induce much degradation in the microwave dielectric properties but lowers the τf value to near zero. Typically, the excellent microwave dielectric properties of ɛr=21.5, Q×f=32 938 GHz, and τf=6.1 ppm/°C could be obtained for the 1 wt% V2O5‐doped sample sintered at 920°C, which is promising for application of the multilayer microwave devices using Ag as an internal electrode.