Preparation, phase structure, sintering behavior, and microwave dielectric properties of LiBiW2O8 ceramic have been investigated. The LiBiW2O8 ceramic can be well densified in the temperature range from 650° to 750°C for 2–8 h. X-ray diffraction data show that LiBiW2O8 ceramic has a monoclinic structure coupled with a second unknown phase. The LiBiW2O8 ceramic, sintered at 700°C for 2 h, exhibit microwave dielectric properties with permittivity of 26.5, Q×f of 16400 GHz, and temperature coefficient of resonant frequency (τf) of 70 ppm/°C. The addition of 30 mol% TiO2 to LiBiW2O8 also results in a ceramic composite exhibiting ɛr∼30.2, Q × f∼13 000 GHz and τf∼−9 ppm/oC. However, the reaction between LiBiW2O8 and Ag will affect its further application in low-temperature cofired ceramic.