Electrochemical properties of micro-size spherical TiO2(B) secondary particles have been investigated in order to develop TiO2(B) anodes for lithium-ion batteries with high-power and long-life performance. The spherical TiO2(B) electrodes with a small amount of a carbon conductor additive had a high electrode density of 2.2 g cm−3 and a volumetric reversible capacity of 475 mAh cm−3 comparable to that of graphite electrodes. Compared with nano-size needle-like TiO2(B) electrodes, the spherical TiO2(B) electrodes exhibited higher-rate discharge capability and longer-cycle life performance. The impedance of the TiO2(B)/electrolyte interface model indicated that the charge transfer resistance R c and the passivating film resistance R f of the spherical TiO2(B) were much smaller than those of the needle-like one. The high-rate discharge and the long-cycle performance of the spherical TiO2(B) electrode are attributed to the superior electronic connective property and R c and R f values smaller than those of the needle-like one. Lithium-ion cells using the spherical TiO2(B) anodes and LiNi0.8Co0.1Mn0.1O2 cathode with a capacity of 2.8 Ah exhibited a high energy density of 100 Wh kg−1, a high output power density of 1800 W kg−1 for 10 s pulse, and a long cycle life of more than 3000 cycles.