Transition metal oxides anodes of lithium ion batteries (LIBs) usually suffer from low reaction kinetics with slow charge/ions transfer resulting from severe volume variation. In this work, thin porous copper shell is homogeneously coated on the CoO nanowires forming CoO/Cu hetero-structured arrays. Cu shell not only acts as a conductive network, but also serves as a protective “armor” layer to keep electrode stable upon cycling. Meanwhile, 3D porous architecture with large surface area is well preserved in the CoO/Cu hetero-structured arrays. Due to enhanced electron/ion transfer characteristics and strengthened electrode structure, the as-prepared CoO/Cu hetero-structured arrays exhibit much higher electrochemical reactivity with lower polarization and better reversibility due to the introduction of thin Cu shell. Additionally, enhanced discharge capacity and large-rate performances are also demonstrated in the CoO/Cu hetero-structure arrays when compared with the pure CoO nanowires counterpart.