An original carbothermal synthesis of ramsdellites phases under specific atmosphere (Ar, Ar/H-2, N-2. N-2/H-2) allowed creating in situ composites which showed good electrochemical properties as negative active materials of Li-ion batteries. The combination of chemical, XRD and electrochemical analyses enabled to identify the as-formed composite electrodes. It consists in ramsdellite/spinel for the synthesis under Ar/H-2, TiO2 ramsdellite/Li2TiO3 for the synthesis under N-2/H-2, and Li2 +/- xTi3O7/Li2 yTi307 for the samples prepared under both N2 and Ar. Carbon is partially inserted inside channels of titanate structure for the sample obtained under Ar/H2. For the first time, one of these composites allowed reaching a specific capacity close to the theoretical value of 198 mAh (C) 2010 Elsevier Ltd. All rights reserved.