A new Li2O–Nb2O5–TiO2 (LNT) ceramic with the Li2O:Nb2O5:TiO2 mole ratio of 3:1:3 has been investigated. The compound is composed of two phases, the Li2TiO3 and “M-phase” solid solution phase. The microwave dielectric ceramic has low sintering temperature (∼1100 °C) and good microwave dielectric properties of a relatively high permittivity (∼51), high Q × f value up to 8700, and small temperature coefficient (∼37 ppm/°C). The low-amount doping of 0.83Li2O–0.17V2O5 (LV) can effectively lower the sintering temperature from 1100 to 900 °C and induce no obvious degradation of the microwave dielectric properties. Typically, the 1 wt.% LV-doped ceramic sintered at 900 °C has better microwave dielectric properties of εr = 51.3, Q × f = 7235 GHz, τ f = 22 ppm/°C, which suggests that the ceramics can be applied in microwave LTCC devices.