Li 2 TiO 3 -based materials are gaining momentum in the field of microwave dielectric ceramics for their moderate dielectric constant and high-quality factor. Herein, a novel oxyfluoride ceramic Li 3 TiO 3 F in the Li 2 TiO 3 –LiF system was successfully prepared by a traditional ceramic method. The synthesis process of Li 3 TiO 3 F ceramic was optimized to obtain improved microstructure and desired microwave dielectric properties (MDP) by means of material characterization techniques, such as thermogravimetric-differential thermal analysis, X-ray diffraction, scanning electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. A cubic rock salt structure for Li 3 TiO 3 F ceramic was confirmed by Rietveld refinement results. The ceramic sintered at 900 °C showed the most favorable MDP of ε r = 17.28, quality factor (Q × f) = 96,280 GHz, and τ f = −32.7 ppm/°C, obtaining a microstructure superior to that of Li 2 TiO 3. Moreover, the ceramic exhibited favorable chemical compatibility with Ag at 900 °C, indicating a great potential for the use of Li 3 TiO 3 F ceramic as substrates in low temperature cofired ceramic (LTCC) technology. More importantly, the results of this work offered the option of using low temperature firing of ceramic by forming a solid solution between the oxide and the fluoride. [ABSTRACT FROM AUTHOR]