A Li₄WO₅ ceramic with rock salt structure was prepared by the solid-state reaction method and its microwave dielectric properties was demonstrated for the first time. It could be well densified at relatively low sintering temperature (~890°C). XRD and DTA analysis revealed a phase transformation from cubic to orthorhombic occured at 700°C. Excellent microwave dielectric properties with a near-zero temperature coefficient of resonant frequency ~-2.6ppm/°C, a relative permittivity ~8.6 and a quality factor ~23,100GHz (at 11.0GHz) was obtained. Li₄WO₅ was found to be chemically compatible with silver powders when sintered at 890°C. All the results indicate that the Li₄WO₅ ceramic is a promising candidate as a base material in low temperature cofired ceramic technology.