Tremella-like V₂O5 microspheres were successfully synthesized in this study through a facile hydrothermal method. The microstructures and electrochemical properties were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) measurements and galvanostatic charge-discharge tests. V₂O5 microspheres with unique tremella-like structure exhibited good reversible capacity, with an initial discharge capacity of 147 mA·h·g-1 at 1 C rate. Moreover, the capacity retention rate was 91.36% and charge-discharge efficiency was still over 98% after 400 cycles. Such outstanding properties can be ascribed to their unique tremella-like structure.