A one-pot and template-free solvothermal method was developed to synthesize the hierarchical WO3 hollow microspheres with porous shells. The porous shell of as-synthesize WO3 hollow microspheres are constructed from primary nanoplates clusters of 50nm. The as-synthesize WO3 hollow microspheres are not monodisperse, and most of hollow microspheres are interconnected by sharing one wall. Importantly, the as-synthesize WO3 hollow microspheres exhibit excellent electrochemical performance. At current density of 100mAg−1, they can deliver a specific capacity of 1700mAhg−1 in the first discharge and retain a specific capacity of 700mAhg−1 after 100 cycles. Meanwhile, even at a high current density of 1600mAg−1, they also exhibit a specific capacity of 213mAhg−1 after 500 cycles. This superior electrochemical performance of the as-synthesized WO3 hollow microspheres could be ascribed to its unique hierarchical architecture.