Spinel Li4Ti5O12 nanoparticles were prepared via a high-temperature solid-state reaction by adding the prepared cellulose to an aqueous dispersion of lithium salts and titanium dioxide. The precursors of Li4Ti5O12 were characterized by thermogravimetry and differential scanning calorimetry. The obtained Li4Ti5O12 nanoparticles were characterized using X-ray diffraction, transmission electron microscopy (TEM) and electrochemical measurements. The TEM revealed that the Li4Ti5O12 prepared with cellulose is composed of nanoparticles with an average particle diameter of 20–30 nm. Galvanostatic battery testing showed that nano-sized Li4Ti5O12 exhibit better electrochemical properties than submicro-sized Li4Ti5O12 do especially at high current rates, which can deliver a reversible discharge capacity of 131 mAh g−1 at the rate of 10 C, whereas that of the submicro-sized sample decreases to 25 mAh g−1 at the same rate (10 C). Its reversible capacity is maintained at ~172.2 mAh g−1 with the voltage range 1.0–3.0 V (vs. Li) at the current rate of 0.5 C for over 80 cycles.