[en] Vanadium oxide (V₂O₅) microspheres have attracted considerable attention in the energy field due to their unique properties such as high stability and electrochemical activity. Here, massive V₂O₅ microspheres with smooth surface, hollow cavity and uniform particle sizes (0.4–1.5 μm), were synthesized by a facile spray pyrolysis process. Post-treatment at predefined temperatures effectively turned the microsphere shell into stacked nanorods with widths of 100 nm and lengths of 500 nm when processed at 500 °C for 3 h under nitrogen atmosphere, with enhanced crystallinity. When applied as cathode materials for supercapacitors, the post-treated V₂O₅ microspheres at 500 °C exhibited improved specific capacitance and longer discharge time. This is an effective method to manufacture massive V₂O₅ microspheres with tailored structure and potential applications in high-performance energy storage materials. (paper)