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 degrees C and exhibits good microwave dielectric properties with permittivity (epsilon(r)) of 25.4, high Qxf value about 39000GHz, and low temperature coefficient of resonate frequency ((f)) of 10ppm/degrees C. The addition of BaCu(B2O5) can effectively lower the sintering temperature from 1120 degrees C to 900 degrees 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.