Zn2+ and F- ions are successfully used to modify pure Li4Ti5O12 via a co-precipitation method followed by calcination at 400 degrees C for 5 h in an Ar atmosphere in order to further investigate the reaction mechanism of the Fluoride modification process. Zn2+ and F- co-modified Li4Ti5O12 samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. After the modification process, no ZnF2 coating layer is formed on the surface of Li4Ti5O12, instead, F- ions react with Li4Ti5O12 to generate a new phase, composed of a small amount of anatase TiO2, rutile TiO2, LiF, and Zn2+ ions are suspected to form a ZnO coating layer on Li4Ti5O12 particles. The electrolyte reduction decomposition is suppressed in Zn2+ and F- co-modified Li4Ti5O12 due to the ZnO coating layer. 1 wt.% Zn2+ and F- co-modified Li4Ti5O12 exhibits the best rate capability, which leads to a charge capacity of 236.7, 227.8, 222.1, 202.7, 188.9 and 150.7mAh g(-1) at 0.2C, 0.5C, 1C, 3C, 5C and 10C, respectively, between 0V and 3V. Furthermore, 1 wt.% Zn2+ and F- co-modified Li4Ti5O12 exhibits 96.0% charge capacity retention at 3C rate after 200 cycles, which is significantly higher than that of pure Li4Ti5O12 (78.4%).