Macroporous TiO2 was synthesized by using low-cost bio-ingredients as the pore forming templates. TiCl4 in C2H5OH(l) containing NH4OH(aq.) was polymerized in the presence of instant yeast and glucose. The organic-inorganic hybrid precursor was further processed to generate macroporous anatase TiO2 (pore size: 2.5-3 μm) with mesopores (4-51 nm). The porous TiO2 was coated with a thin layer of carbon by chemical vapour deposition to generate the hierarchical C/TiO2 nanocomposite material. The porous products were investigated as anode materials for Li-ion batteries. The capacities of the hierarchical C/TiO2 electrode material remained 180 mA h g-1 and 142 mA h g-1 under high charge/discharge rates of 5 C and 10 C, respectively. It demonstrated good cycling stability of 318 mA h g-1 at 0.1 C at various discharge-charge rates. The excellent performance is attributed to the high specific surface areas and open spaces of the C/TiO2 allowing effortless intercalation/deintercalation of Li ions.