Understanding the formation of SEI films on Li4Ti5O12 (LTO) anodes offers a major benefit to large-scale applications of lithium ion batteries made therefrom. This paper reveals that an SEI film is formed above 1 V due to the interfacial reaction between the electrode and electrolyte: LTO anodes are previously considered free from SEI films when cycled between 1 and 3 V. The reactivity and the formation of SEI films are much affected by the morphology and surface area of the electrode. To study the above, LTO powders with different morphologies are synthesized using lithium acetate (LA) and lithium hydroxide (LH) as the lithium sources. LTO–LH consisting of agglomerates of primary small particles with a large surface area has higher reactivity than LTO–LA with a cubic structure and small surface area. As a result, the LTO–LH anode with a smooth SEI film offers better cyclic performance than the LTO–LA anode with a porous SEI film. The addition of vinylene carbonate to the electrolyte facilitates rapid formation of a protective SEI film on LTO–LA, greatly improving the rate and cyclic performance: stable specific capacity of 155.6 mAh g−1 and remarkable 135.2 mAh g−1 after 500 cycles at 10 C are recorded.