The effect of high-energy ball milling (HEBM) on the synthesis and sintering of Li2TiO3 was investigated. XRD Phase analysis of milled powders revealed a common phenomenon of peak broadening due to crystallite size reduction and loss of long-range periodicity. Thermal analysis results showed that the formation of Li2TiO3 can be facilitated with high-energy ball mill. Density measurement of sintered parts revealed that milling time of 5 h (HEBM-5) is sufficient to achieve a high density of 3.19 g/cm3 (93.82% of the theoretical density) at low sintering temperature of 1100 °C. The average particle size of synthesized Li2TiO3 powder was about 150 nm. SEM observations revealed the achievement of dense microstructures with abnormal grain growth. Optimal dielectric constant of e r = 21.85, Q × f = 17510 GHz and τ f value of + 26 ppm/°C were achieved. Li2TiO3 was also synthesized without high-energy milling and sintered at 1100 °C and the density of 3.03 g/cm3 (89.11% of theoretical density) was achieved.