To accelerate the development of lithium-ion batteries (LIBs), researchers should urgently exploit next-generation electrodes with high specific capacity, long cycle stability, and excellent rate performance, such as TMOs, silicon-based materials, and alloys. Among all the modification measures, hierarchical micro-nano structure and yolk–shell structure are considered suitable and effective ways to improve the electrochemical performance of those novel materials. Herein, a facile glucose-assisted solvothermal method combined with heat treatment was implemented to synthesize hierarchical micro-nano yolk–shell V2O3. The special-structured material exhibited higher specific capacity, better structure stability, and faster electrochemical kinetics compared with nanosheet-structured and micro-nano-cluster-structured V2O3. When used as an anode for LIB, mnYS-V2O3 delivered high specific capacity of 650.1 mA h g−1 after over 500 cycles at a current density of 100 mA g−1, with a retention of 93.4 %. Moreover, the morphology evolution mechanism of micro-nano structure and yolk–shell structure was investigated in this work, which is beneficial to the design of other mnYS-structured TMOs.