Li2O–MgO–TiO2 ternary system is an important microwave dielectric ceramic material with excellent properties and prospect in both scientific research and application. A phase diagram of the Li2O–MgO–TiO2 ternary system was established in this article, based on earlier research results and our present work. Microwave dielectric properties with compositions in different regions of the phase diagram have been analyzed. We found that the 0.33 Li2MgTi3O8–0.67 Li2TiO3 ceramics sintered at 1200°C exhibited excellent dielectric properties: Q × f value = 80 476 GHz (at 7.681 GHz), εr = 24.7, τf = +3.2 ppm/°C. We also designed two ceramic systems in the Li‐rich region of the Li2O–MgO–TiO2 ternary system, which received little attention in the past decades, because many excellent single‐phase ceramics, such as Li2MgTiO4, Li2MgTi3O8 and MgTiO3, have been found in the Ti‐rich region. The ceramic systems have low sintering temperatures but also relatively poor dielectric properties.