TiO2 with the ramsdelitte-type (R) structure has a potential use as negative electrode for Li-ion battery due to its high theoretical capacity (335mAhg−1), a weak irreversible loss during the first cycle and a low polarization. However due to its metastability, TiO2 (R) has been rarely reported. In the present work we report on the carbothermal synthesis of some Li x TiO2 delithiated R phases (0< x <0.57), from TiO2 to Li2Ti3O7, with ramsdellite-type structure. The variation of the synthesis parameters such as wt% of carbonaceous additive and reductive gas flow has conducted to the formation of poor lithiated Li x TiO2 phases and Li2TiO3 as additional phase. Their ratio was found to be strongly dependent on the amount of carbonaceous precursor. These new Li x TiO2(R)/Li2TiO3 composites (with (0≤ x ≤0.57)) were characterized by chemical analysis, X-ray diffraction and thermogravimetric analysis and finally by electrochemical tests. High capacities as well as good cycleability have been reached.