Novel hierarchical porous TiO2(B)/anatase microspheres have been prepared by a facile solvothermal approach and evaluated as anode materials for advanced lithium-ion battery applications. The obtained porous microspheres, with diameters ranging from 2.5 to 5.5μm, are assembled by porous TiO2 nanosheets with the lateral size of a few micrometers and thickness of ~13nm; whilst, the nanosheets are formed by aggregations of nanosized primary TiO2 crystallites (~5–7nm). The hierarchical porous structures are verified by BET test results with a typical type-IV isotherm curve, a high surface area (~186.2m2 g−1) and two kinds of pores (~4 and 8.3nm). The hierarchical porous TiO2 microspheres present excellent electrochemical performance with high Li storage capacity and excellent high-rate cycling capability (a specific capacity of 117mAhg−1 at the rate of 4000mAg−1 after 4500 cycles), which might be attributed to the enhanced Li+ diffusion and electronic conductivity induced by the hierarchical microstructures, the TiO2(B)/anatase heterojunction, and the pseudocapacitance of TiO2(B). Such hierarchical porous materials might be promising for applications in advanced power type lithium-ion batteries.