Li4Ti5O12 was synthesized by a modified and facile sol–gel method with ethylene diamine tetraacetic acid (EDTA) and citric acid (CA) as a bi-components chelating agent. The raw precursor and powders further calcined at various temperatures and holding time were characterized by XRD, FT-IR, TG, BET and SEM. Nano-scale Li4Ti5O12 oxides, with a high phase purity and good stoichiometry, can be obtained at a calcination temperature of 750 °C and higher. The Li4Ti5O12 nanoparticle shows a network morphology with high dispersion, which reached a capacity of 164 and 108 mAh g−1 at 1C and 10C discharge rate, respectively. The result of the cycling performance shows a high capacity maintenance ratio of 97% at 1C and 25 °C after 1000 cycles. Electrochemical lithium intercalation/extraction performance is also evaluated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) at room temperature.