[en] In this work, flower-like hierarchical Nb₂O₅ microspheres self-assembled by nanorod with orthorhombic (T) phase were synthesized using hydrothermal method. The structure and morphology of T-Nb₂O₅ prepared is characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The structure and morphology evolution mechanisms have been preliminarily proposed for the flower-like hierarchical structure. The electrochemical performances of T-Nb₂O₅ electrodes synthesized are detailed studied for use in LIBs and HSC devices. The T-Nb₂O₅ anode exhibits the reversible capacity of 191.42 mA h g⁻¹ at 0.05 A g⁻¹ and excellent rate performance (90.01 mA h g⁻¹ at 5A g⁻¹) in the voltage of 1.1–3.0 V (vs Li/Li⁺). The HSC using T-Nb₂O₅ anode and activated carbon cathode device delivers outstanding power density and energy density (8750 W kg⁻¹ and 40.25 W h kg⁻¹) with good stability in the voltage of 0.5–3.0 V. - Highlights: • Flower-like hierarchical Nb₂O₅ microspheres are synthesized via hydrothermal method. • The T-Nb₂O₅ anode exhibits the capacity of 191.42 mA h g⁻¹ at 0.05 A g⁻¹ • The discharge capacity of T-Nb₂O₅ anode is 90.01 mA h g⁻¹ at 5 A g⁻¹ • The T-Nb₂O₅//AC-based HSC system shows outstanding electrochemical performance.