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We report the preparation of porous CuO nanowires that are composed of nanoparticles (~50 nm) via a simple decomposition of a Cu(OH)2 precursor and their application as the anode materials of rechargeable Na-ion batteries. The as-prepared porous CuO nanowires exhibit a Brunauer–Emmett–Teller (BET) surface area of 13.05 m2·g−1, which is six times larger than that of bulk CuO (2.16 m2·g–1). The anode of porous CuO nanowires showed discharge capacities of 640 mA·h·g–1 in the first cycle and 303 mA·h·g–1 after 50 cycles at 50 mA·g–1. The high capacity is attributed to porous nanostructure which facilitates fast Na-intercalation kinetics. The mechanism of electrochemical Na-storage based on conversion reactions has been studied through cyclic voltammetry, X-ray diffraction (XRD), Raman spectroscopy, and high resolution transmission electron microscopy (HRTEM). It is demonstrated that in the discharge process, Na+ ions first insert into CuO to form a
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