Rational design/fabrication of integrated porous metal oxide arrays is critical for the construction of advanced electrochemical devices. Herein, we report self-supported CuO/C core/shell nanowire arrays prepared by the combination of electro-deposition and chemical vapor deposition methods. CuO/C nanowires with diameters of ~400 nm grow quasi-vertically to the substrates forming three-dimensional arrays architecture. A thin carbon shell is uniformly coated on the CuO nanowire cores. As an anode of lithium ion batteries, the resultant CuO/C nanowire arrays are demonstrated to have high specific capacity (672 mAh·g−1 at 0.2 C) and good cycle stability (425 mAh·g−1 at 1 C up to 150 cycles). The core/shell arrays structure plays positive roles in the enhancement of Li ion storage due to fast ion/electron transfer path, good strain accommodation and sufficient contact between electrolyte and active materials.