W-doped Li4Ti5O12 (LTO) in the form of Li4Ti5−x W x O12 (x =0.05, 0.1, 0.15 and 0.2) is prepared by sol–gel method and following two-step calcinations in the air and argon atmosphere, respectively. The as-prepared samples are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). XRD analysis demonstrates that W6+ can successfully enter the structure of cubic spinel-type LTO, increase the lattice parameter and no impurities appear. XPS results further identify the existence of W6+ ion. SEM images show that all samples had similar particulate morphologies and the particle size distribution was in the range of 0.5–1μm. The results of electrochemical measurement reveal that W-doping can improve the rate capability of LTO. However, heavy W substitution causes a discharge capability loss. The electronic conductivity of Li4Ti4.9W0.1O12 powder is as high as 1.5×10−1 Scm−1, which is much higher than 10−13 Scm−1 of the pristine LTO. The Li4Ti4.9W0.1O12 electrode exhibits the best rate capability and cycling stability, and its discharge capacity at 10C is 128.1mAhg−1 after 100 cycles. The Li4Ti4.9W0.1O12 sample stands as a promising potentially high rate anode material for lithium-ion batteries.