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[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.