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We report the facile, one-pot synthesis of 3-D urchin-like W18O49 nanostructures (U-WO) via a simple solvothermal approach. An excellent supercapacitive performance was achieved by the U-WO because of its large Brunauer–Emmett–Teller (BET) specific surface area (ca. 123 m2·g–1) and unique morphological and structural features. The U-WO electrodes not only exhibit a high rate-capability with a specific capacitance (Csp) of ~235 F·g–1 at a current density of 20 A·g–1, but also superior long-life performance for 1, 000 cycles, and even up to 7, 000 cycles, showing ~176 F·g–1 at a high current density of 40 A·g–1.