The carbon-coated TiO2 (TiO2@C) and FeTiO3 (TiO2/FeTiO3@C) hybrid porous microspheres with a specific surface area of 35.1 m2g−1 have been successfully synthesized by carbonizing the mixture of pyrrole with lab-made TiO2/Fe2O3 porous microspheres. The as-prepared TiO2/FeTiO3@C porous electrode material possessed a reversible capacity of 441.5 mAh g−1 after 300 cycles at a current density of 100mAg−1 and a coulombic efficiency of 99%. Comparing with TiO2, TiO2@C, and TiO2/Fe2O3 porous microspheres, the TiO2/FeTiO3@C porous composites exhibited superior cycling and rate performances, which are rooted in the synergistic effect that generated by little volume variation of TiO2 matrix, high capacity of FeTiO3 and good electrical conductivity of carbon coating (with a thickness of 2–5nm deposited on the surface and inner wall of pores) during the charge/discharge processes.