Currently, developing materials with high power capability is crucial to the rapid deployment of electric vehicles. The Li4Ti5O12 (LTO) anode material with zero strain rate upon lithium insertion and extraction. The successful implementation of this anode material depends on strategies to overcome the low electronic and ionic conductivity. In this study, Li4Ti5O12 was synthesized using solid‐state approach in which different phases (anatase and rutile) of TiO2 as precursors were used. X‐ray photoelectron spectroscopy (XPS) and Raman analysis confirmed the formation of oxygen vacancies with the existence of Ti3+ ions, which is believed to greatly enhance the electronic conductivity of Li4Ti5O12. The electrochemical performance revealed that the rutile TiO2 precursor concentration significantly affects the resultant Li4Ti5O12 capacity and power capability. The Li4Ti5O12 synthesized using 80% anatase and 20% rutile TiO2 (N2‐LTO) exhibits a specific capacity of 169, 145, 140, 133, 122, 101, and 84 mAh g−1 at 1C, 3C, 5C, 7C, 10C, 20C, and 30C. In addition, LFP||N2‐LTO pouch‐cell was fabricated which showed promising results with 95% capacity retention after 1000 cycles at 1C rate. The oxygen vacancies created due to the presence of Ti3+/Ti4+ mixed valances and reduced particle size for faster lithium‐ion diffusion significantly enhanced the overall electrochemical performance.