We have reported for the first time the preparation of yolk–shell-structured Li4Ti5O12 powders for use as anode materials in lithium-ion batteries. One Li4Ti5O12 yolk–shell-particle powder is directly formed from each droplet containing lithium, titanium, and carbon components inside the hot wall reactor maintained at 900 °C. The precursor Li4Ti5O12 yolk–shell-particle powders, which are directly prepared by spray pyrolysis, have initial discharge and charge capacities of 155 and 122 mA h g−1, respectively, at a current density of 175 mA g−1. Post-treatment of the yolk–shell-particle powders at temperatures of 700 and 800 °C improves the initial discharge and charge capacities. The initial discharge capacities of the Li4Ti5O12 powders with a yolk–shell structure and a dense structure post-treated at 800 °C are 189 and 168 mA h g−1, respectively. After 100 cycles, the corresponding capacities are 172 and 152 mA h g−1, respectively (retentions of 91 and 90 %).