Li4Ti5O12 is a very promising anode material for lithium secondary batteries. A novel technique has been developed to prepare Li4Ti5O12. The spherical precursor is prepared via an “inner gel” method by TiCl4 as the raw material. Spherical Li4Ti5O12 powders are synthesized by sintering the mixture of spherical precursor and Li2CO3. The investigation of XRD, SEM and the determination of the electrochemical properties show that the Li4Ti5O12 powders prepared by this method are spherical, and have high tap-density and excellent electrochemical performance. It is tested that the tap-density of the product is as high as 1.64gcm−3, which is remarkably higher than the non spherical Li4Ti5O12. Between 1.0 and 3.0V versus Li, a reversible capacity is as high as 161mAhg−1 at a current density of 0.08mAcm−2.