A new Li-containing microwave ceramic Ba5Li2W3O15 with hexagonal perovskite structure was prepared through a solid-state ceramic route. Small amount of scheelite BaWO4 appeared as a second phase during sintering. The Ba5Li2W3O15 could be well densified at 1120°C and exhibits good microwave dielectric properties with permittivity (εr) of 25.4, high Q × f value about 39 000 GHz, and low temperature coefficient of resonate frequency (τf) of 10 ppm/°C. The addition of BaCu(B2O5) can effectively lower the sintering temperature from 1120°C to 900°C and does not induce degradation of the microwave dielectric properties. These results indicate that the Ba5Li2W3O15 ceramic might be a promising candidate in microwave dielectric resonators.