Abstract The spinel Li[Li 1/3Ti 5/3]O 4 compound was synthesised via a solid-state method and its electrochemical performance in lithium ion cells was examined. Lithium ions intercalate into and deintercalate from Li[Li 1/3Ti 5/3]O 4 with high reversibility. The spinel Li[Li 1/3Ti 5/3]O 4 demonstrated a very stable structural characteristic for lithium ion insertion and extraction without passivation on its surface. The spinel Li[Li 1/3Ti 5/3]O 4 as an anode material was coupled with LiCoO 2 and LiMn 2O 4 as cathodes to construct lithium ion cells. These cells provide 2.4–2.5 V operating voltage and without the safety concerns associated with using lithium metal or carbon anodes.