Nanotube arrays have shown great potential in a variety of important applications, such as energy storage. To enhance their inherent properties and endow nanotubes with multifunctionality, the rational design of nanotube arrays with higher complexity in terms of structure and composition is highly desired and still remains a great challenge. In this work, Ni@NiO core–shell nanoparticle tube arrays (CSNPTAs) were designed and fabricated via an efficient, low-cost and environmentally friendly ZnO nanorods template-assisted electrodeposition method, and they are effective in enhancing ion diffusion and surface area as well as preventing nanoparticle agglomeration because of the unique array structures, hollow structures, and core–shell nanoparticle structures. As electrodes, Ni@NiO CSNPTAs show high electrochemical performance such as high specific capacitance (C_sp), superior rate capability, and excellent cycle stability and exhibit promising applications for high-performance supercapacitors (SCs).