Li 2 Ti 6 O 13 has been prepared from Na 2 Ti 6 O 13 by Li ion exchange in molten LiNO 3 at 325°C. Chemical analysis and powder X-ray diffraction study of the reaction product respectively indicate that total Na/Li exchange takes place and the Ti–O framework of the Na 2 Ti 6 O 13 parent structure is kept under those experimental conditions. Therefore, Li 2 Ti 6 O 13 has been obtained with the mentioned parent structure. An important change is that particle size is decreased significantly which is favoring lithium insertion. Electrochemical study shows that Li 2 Ti 6 O 13 inserts ca. 5 Li per formula unit in the voltage range 1.5–1.0V vs. Li + /Li, yielding a specific discharge capacity of 250mAhg −1 under equilibrium conditions. Insertion occurs at an average equilibrium voltage of 1.5V which is observed for oxides and titanates where Ti(IV)/Ti(III) is the active redox couple. However, a capacity loss of ca. 30% is observed due to a phase transformation occurring during the first discharge. After the first redox cycle a high reversible capacity is obtained (ca. 160mAhg −1 at C/12) and retained upon cycling. Taking into consideration these results, we propose Li 2 Ti 6 O 13 as an interesting material to be further investigated as the anode of lithium ion batteries.