In this work, Li4Ti5O12 (LTO) was synthesized from the precursors of TiO2-B and anatase whiskers, respectively. The synthesized LTO whiskers from TiO2-B whiskers via a solid state reaction at 650°C have a high degree of crystallinity with an average diameter of 300nm. However, when anatase whiskers were used as the precursor, only particle morphology LTO was produced at 750°C. The further analysis of the precursors, the intermediate products and the final products reveal that the crystal structure of the anatase hinders the diffusion of lithium, leading to a typical reaction–diffusion process. Under this condition, only particle morphology LTO can be produced. However, the crystal structure of the TiO2-B is easy for lithium diffusion and the process is performed in two separated steps (i.e., diffusion and reaction), which makes it possible to decrease the solid-state reaction temperature down to 650°C and then maintain the morphologies of whiskers.