Li[Li1/3 Ti5/3 O4] spinel-framework structure material is a kind of great interest for negative electrodes in energy storage cell. The synthesis of nanocrystalline Li[Li1/3 Ti5/3 O4] by sol-gel method using inorganic compounds and citric acid is developed, and single phase powder is obtained above 700 ℃. The electrochemical performances of Li[Li1/3Ti5/3O4] cathodes in lithium cell are studied. Special capacities are 131 mA · h · g-1 at 0.5C rate and 154 mA · h · g-1 at 0.1C in cycle test. No passivation layer is formed on Li[Li1/3Ti5/3O4] anode in lithium ion battery, and it is much safer than lithium metal and carbonaceous anodes. Faradic impedance in the charged cell is remarkably higher than that in discharged state, which is caused by distinct conductivities of Li [ Li1/3 Ti5/3 O4 ] and Li2 [Li1/3 Ti5/3 O4 ].