Commercial Li4Ti5O12 is modified by AlF3 with the purpose of suppressing the gas generation of Li4Ti5O12 anode battery. The prepared AlF3-modified Li4Ti5O12 is characterized by a variety of means such as X-ray diffraction, scanning electron microscope, transmission electron microscope and X-ray photoelectron spectroscopy. The results indicate that only part of Al3+ and F− have co-doped into the bulk phase of Li4Ti5O12 particles, while the rest of the Al3+ and F− remain on the surface of the Li4Ti5O12 particles to form an AlF3 coating layer. The AlF3 coating layer on the surface of AlF3-modified Li4Ti5O12 is very effective in suppressing the gas generation of Li4Ti5O12 anode battery. AlF3 modification is a simple yet very effective strategy, which can both improve the high-rate charge/discharge performance of Li4Ti5O12 and suppress the gassing behavior of Li4Ti5O12 anode battery.