The cave-embedded porous Mn2O3 hollow microsphere is synthesized from aqueous manganese chloride by a facile one-step spray pyrolysis. When evaluated as anode materials for LIBs, the as-obtained Mn2O3 microsphere easily allows the electrolyte to penetrate into the hollow interior through the cave, providing more active sites and a shortened Li+ diffusion pathway. As a result, the enhanced charge transfer and lithium ion diffusion kinetics is achieved. Furthermore, the special structure is able to mitigate the stress led by enormous volume variation and maintain the structural integrity during conversion reaction process. Benefiting from the special structural features, the Mn2O3 microspheres with such smart architecture delivers a reversible capacity of ∼1000mAhg−1 at 300mAg−1 after 100th cycle, and maintains a high reversible capacity of 639mAhg−1 at 1600mAg−1, showing better electrochemical performance than the conventional Mn2O3 microspheres.