Porous TiNb2O7 nanospheres comprised of nanoparticles have been synthesized with the assistance of block copolymer P123 (EO20PO70EO20). Such porous TiNb2O7 nanospheres, with diameter of 500nm, exhibit a BET surface area of 23.4m2/g and pore volume of 0.155cm3/g. As the anodes for lithium-ion batteries, the TiNb2O7 nanospheres present a reversible capacity of 160mAh/g after 10000 cycles at 5C with a capacity loss of only 0.0033% per cycle, and good rate performance of 167mAh/g at 50C. Furthermore, the TiNb2O7 materials still maintain the morphology of nanospheres and the porous structure even after 10000 cycles.