AbstractThe phase equilibria of the pseudo-binary Li2O–TiO2 system and the stoichiometry shift of Li2TiO3 during the Li transmutation process are investigated. The structural properties, the thermal expansion, enthalpy, heat capacity, enthalpy of transformation and melting, thermal conductivity and the vapourisation behaviour of Li2TiO3 are assessed. The ternary Li–Ti–O system is treated with emphasis to the characteristic of Li2TiO3 under reducing conditions. The phase is reduced to LiTiO2 with the Ti valence +3 due to its transition metal character.