Abstract In order to solve the problems of acceptor/donor individual doping in Li 2 TiO 3 system and clarify the superiority mechanism of co‐doping for improving the Q value, Mg + Nb co‐doped Li 2 TiO 3 have been designed and sintered at a medium temperature of 1260°C. The effects of each Mg/Nb ion on structure, morphology, grain‐boundary resistance and microwave dielectric properties are investigated. The substitution of (Mg 1/3 Nb 2/3 ) 4+ inhibits not only the diffusion of Li + and reduction in Ti 4+ , but also the formation of microcracks in ceramics, which promotes the enhancement of Q value. The experiments reveal that Q × f value of Li 2 TiO 3 ceramics co‐doped with magnesium and niobium is 113 774 GHz (at 8.573 GHz), which is increased by 113% compared with the pure Li 2 TiO 3 ceramics. And the co‐doped ceramics have an appropriate dielectric constant of 19.01 and a near‐zero resonance frequency temperature coefficient of 13.38 ppm/°C. These results offer a scientific basis for co‐doping in Li 2 TiO 3 system, and the outstanding performance of (Mg + Nb) co‐doped ceramics provides a solid foundation for widespread applications of microwave substrates, resonators, filters and patch antennas in modern wireless communication equipments.