Li2Co2Mo3O12 (LCMO) ceramics were synthesized using the solid‐state reaction method. XRD analysis results indicated that the sole crystalline phase present in the ceramics was Li2Co2Mo3O12, which belongs to the orthorhombic structure of the Pnma space group. The sample, which was sintered at 850°C, demonstrated outstanding microwave dielectric properties, with an εr value of 8.95, a Q × f value of 43200 GHz, and a τf value of ‐71.3 ppm/°C. It was found that while the main factor influencing εr was ionic polarizability, sintering density had a lesser effect on it. Furthermore, Q × f was primarily affected by relative density, and there was no significant relationship between packing fraction and this property. The higher the degree of distortion of [Li/CoO6] octahedron, the poorer the τf value of LCMO ceramics. Additionally, the microwave dielectric properties of LCMO ceramics were intrinsically linked to ionicity, lattice energy, bond energy, and thermal expansion coefficient of chemical bonds, with Mo‐O bonds being the primary factor affecting these properties as supported by analysis using chemical bonding theories. Mo‐O bond vibration dominated the Raman spectra. Good chemical compatibility between silver and LCMO ceramics was demonstrated through our co‐firing experiment.This article is protected by copyright. All rights reserved