Li2TiO3 (lithium titanate) is a material of interest in the field of fusion reactors due to its potential application as a tritium breeder material. Because of the extreme working conditions and temperature gradients involved, thermal expansion properties are critical to consider when assessing a material for a fusion reactor. The reactor is subjected to severe neutron flux, high temperature and thermal cycling, which can cause significant stress on the material. A low coefficient of thermal expansion (CTE) of Li2TiO3 is important as it mitigates mechanical stress and minimized the risk of structural damage resulting from thermal cycling. Material degradation, cracking, or delamination might result from a mismatch in CTE between different materials in the reactor. Therefore the estimations of material's thermal expansion properties hold significance for the designing and fabrication of structural material. In this study, Li2TiO3 material was compacted into pellets and high-temperature X-ray diffraction (HT-XRD) was employed to obtain X-ray diffraction patterns from room temperature to 1273 K at 100 K intervals. The lattice parameters (a, b, and c) of Li2TiO3 polycrystals were determined and corresponding unit cell volumes were estimated at each temperature. The thermal expansion percentages for the lattice parameters a, b, and c between room temperature and 1273 K were found to be 1.21%, 1.84%, and 1.83% respectively. The calculated coefficient of thermal expansion (CTE) were determined as 12.5 × 10−6 K−1, 19 × 10−6 K−1, and 18.9 × 10−6 K−1for lattice parameters a, b and c respectively. The crystallographic density at room temperature was estimated to be 3.42 g/cm3. The molar volume was calculated to range between 32.12 and 33.72 cm3/mol from room temperature to 1273 K. Additionally, high-temperature dilatometry was employed to measure the thermal expansion of Li2TiO3, resulting in the estimation of coefficient of thermal expansion. From room temperature to 1290 K, the thermal expansion percentage and mean coefficient of thermal expansion were calculated to be 1.91% and 19.64 × 10−6 1/K, respectively. Furthermore, the temperature dependent mean and instantaneous thermal expansion values were also determined. The differential scanning calorimetry (DSC) method was used to estimate the temperature of the monoclinic to cubic transformation, which was determined to be 1416 K. This paper provides a comprehensive description of the conducted experiments, accompanied by the detailed analysis of the thermal expansion properties derived through the use of High-Temperature X-Ray Diffraction (HT-XRD) and HT-dilatometry (High-Temperature Dilatometry).