Novel porous carbon-coated mixed-phase porous TiO2 (TiO2(B)/anatase) nanosheets/reduced graphene oxide composites (TiO2@C/RGO) are successfully prepared through a facile one-pot solvothermal process followed by subsequent heat treatment in H2/Ar. The as-formed composites have a hierarchical porous structure, involving an average pore size of 28.56nm, a large pore volume of 0.589cm3 g−1 and a desired surface area (136.19m2 g−1). When used as an anode material in LIBs, TiO2@C/RGO exhibits stable cycling performance with a reversible capacity of 272.9mAhg−1 (with the second capacity retention of 151.1%) after 500 cycles at a current density of 100mAg−1, much higher than that of TiO2@C (177.6mAhg−1, 123.9% of the discharge capacity in second cycle) and TiO2 (75.1mAhg−1, corresponding to 96.5% of the original capacity). More impressively, the capacity of TiO2@C/RGO can reach 158.6mAhg−1 after 500 cycles even at 800mAg−1 with Coulombic efficiency above 99.0%. The superior electrochemical performance of TiO2@C/RGO may be attributed to its unique 3D hierarchical porous structures, the existence of carbon, large surface area and extremely reduced diffusion length.