Mesoporous polyaniline/anatase TiO2 composite microspheres with the core–shell structure for lithium-ion battery applications are prepared via a facile hydrothermal route. The structure of as-prepared sample is characterized by electron microscopy (TEM), and scanning electron microscopy (SEM), X-ray diffraction (XRD), and Brunauer–Emmett–Teller (BET) surface area. It is suggested that the formation of the core–shell structure can be designated as a two-step assembly process induced by the polymerization of the aniline. The electrochemical tests demonstrate that the discharge capacity of the as-prepared polyaniline/anatase TiO2 microspheres can be stably retained at 157.1mAhg−1 after 50th cycle at the high current density of 1500mAg−1. The high rate performance of the as-prepared sample at various current densities from 200 to 2000mAg−1 is also investigated. The discharge capacity of 123.9mAhg−1 can be obtained at the high current density of 2000mAg−1, which is about 73.4% of that at the low current density of 200mAg−1 upon cycling, indicating that the as-prepared sample can endure great changes of various current densities to retain a good stability due to the core shell mesoporous structure.