Li₄Ti₅O₁₂/C composite was synthesized by starch-sol-assisted rheological phase method using inexpensive raw material starch as carbon coating precursor. The Li₄Ti₅O₁₂/C powder was characterized using XRD, SEM, and TG techniques. The synthesized Li₄Ti₅O₁₂crystallites are cohesively covered by conductive carbon from starch sol which leads to increased conductivity, and the particle size of Li₄Ti₅O₁₂/C is about 500 nm. The electrochemical performance of Li₄Ti₅O₁₂/C was characterized by galvanostatic charge/discharge and EIS methods, and the results show that the Li₄Ti₅O₁₂/C presents a high discharge capacity, high rate capability, and long cycle life. The capacity retention was at 87% (500 cycles at 1C) and 73.0% (2000 cycles at 20C) indicating promising high rate performance of Li₄Ti₅O₁₂/C as anode material for lithium ion battery.