On the purpose of investigating the influence of calcinations temperature on crystallization and synthesis process of Li4Ti5O12, Li2CO3 and amorphous TiO2 were used as raw materials to synthesize phase Li4Ti5O12 at different calcinations temperatures. TG-DSC showed that the crystallization of the products was more integrated along as temperatures increased. Both anatase and rutile TiO2 would form phase Li2TiO3 by reacting with Li2CO3 primarily before synthesis of phase Li4Ti5O12, and phase Li2TiO3 was formed as mid-phase from 700°C and 750°C revealed in the XRD pattern. SEM demonstrated that the particle size increased as temperature decreased, the particles were agglomerated together especially at 900°C. The samples displayed poor discharge capacity just because of Li2TiO3 phase and large size particles.