Li 4 Ti 5 O 12 /tin phase composites are successfully prepared by cellulose-assisted combustion synthesis of Li 4 Ti 5 O 12 matrix and precipitation of the tin phase. The effect of firing temperature on the particulate morphologies, particle size, specific surface area and electrochemical performance of Li 4 Ti 5 O 12 /tin oxide composites is systematically investigated by SEM, XRD, TG, BET and charge–discharge characterizations. The grain growth of tin phase is suppressed by forming composite with Li 4 Ti 5 O 12 at a calcination of 500°C, due to the steric effect of Li 4 Ti 5 O 12 and chemical interaction between Li 4 Ti 5 O 12 and tin oxide. The experimental results indicate that Li 4 Ti 5 O 12 /tin phase composite fired at 500°C has the best electrochemical performance. A capacity of 224mAhg −1 is maintained after 50 cycles at 100mAg −1 current density, which is still higher than 195mAhg −1 for the pure Li 4 Ti 5 O 12 after the same charge/discharge cycles. It suggests Li 4 Ti 5 O 12 /tin phase composite may be a potential anode of lithium-ion batteries through optimizing the synthesis process.