A general solution method for the oriented growth of large-scale Ni3S2nanowire arrays has been developed. The controlled oxidation scheme by combining ethylenediamine-chalcogens and hydrazine in alkali solution has been shown to have great advantages for the fabrication of metal chalcogenides with fewer instrumental limitations. This method is reliable and works in mild template-free conditions for the production of single-crystalline nanowire arrays. It provides a convenient route for the large-scale growth of pure-phase metal chalcogenide nanowire arrays on metal substrates. The electrochemical measurement results of Ni3S2nanowire arrays for lithium-ion battery electrode applications reveal that they have high reversible lithium storage capacity, long cycle life, good cyclic stability and high charge/discharge rate. With the simplicity of fabrication and good electrochemical performance, Ni3S2nanowire arrays are promising cathode materials for lithium-ion batteries.