Open tunnel-structured TiO2(B) was synthesized by using nanosheets processes. TiO2(B) was obtained only when multi-lamellar tetratitanate nanosheets were used as the reassembly component. The electrochemical properties of the nanosheet-derived TiO2(B) were influenced by guest ions of the self-reassembled nanosheets. When K+ ions were used as guest ions for the self-reassembly of nanosheets, the pure TiO2(B) phase was obtained and it exhibited a large discharge capacity of 253mAh(g-TiO2(B))−1 (x =0.76, Li x TiO2(B)) at a current density of 100mA(g-TiO2(B))−1. This value was a larger than 170mA(g-TiO2(B))−1 of TiO2(B) prepared by a conventional method without the nanosheets process. The large capacity is attributed to an increased specific surface area achieved by the nanosheets process.