Niobium-substituted electrodes have been synthesized by a solid-state method. The structure and electrochemical performance of these as prepared powders have been characterized by differential thermal analysis (DTA) and thermogravimetery (TG), X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and the galvanostatic charge–discharge test. The XRD and RS results show that the can partially replace and in the spinel and there are very few oxygen vacancies in the with a higher electronic conductivity. The Nb-doped lithium titanium oxide samples show smaller particle size and more regular morphology structure, and has the highest initial discharge capacity and cycling performance among all the samples cycled between 0.0 and . CV implies that the niobium doping is beneficial to the reversible intercalation and deintercalation of . EIS indicates that has a smaller charge transfer resistance corresponding to a much higher conductivity than that of corresponding to the extraction of ions. The superior cycling performance and wide discharge voltage range, as well as simple synthesis route and low synthesis cost of the are expected to show a potential commercial application.