The poor electrical conductivity of lithium titanate (Li4Ti5O12) has limited its practical application as high rate performance anode for lithium ion batteries. Having this in mind, we utilize the oxygen vacancy strategy to improve the electrical conductivity of Li4Ti5O12 nanospheres by synthesizing three-dimensional (3D) oxygen-deficient Li4Ti5O12 on a titanium mesh from Ti3+-doped anatase TiO2. When the oxygen-deficient Li4Ti5O12 nanospheres are used as anode material for high-rate lithium ion batteries, the electrode exhibits excellent lithium storage performance delivering a capacity of 143mAhg−1 at a current density of 100C. The outstanding performance is due to the 3D architecture from the 3D substrates with large space and increased surface area that facilitate rapid transfer of lithium ion and small diameter of nanospheres, which provides shorter diffusion path-length.