Developing high-performance electrode structures is of great importance for advanced lithium-ion batteries. This study reports an efficient method to fabricate hierarchical shell/core CuO nanowire/carbon fiber composites via electroless plating and thermal oxidation processes. With this method, a binder-free CuO nanowire/carbon fiber shell/core hierarchical network composite anode for lithium-ion batteries is successfully fabricated. The morphology and chemical composition of the anode are characterized, and the electrochemical performance of the anode is investigated by standard electrochemical tests. Owing to the superior properties of carbon fibers and the morphological advantages of CuO nanowires, this composite anode still retains an excellent reversible capacity of 598.2mAhg−1 with a capacity retention rate above 86%, even after 50 cycles, which is much higher than the CuO anode without carbon fibers. Compared to the typical CuO/C electrode systems, the novel binder-free anode yields a performance close to that of the typical core/shell electrode systems and a much higher reversible capacity and capacity retention than the similar shell/core patterns as well as the anodes with binders. It is believed that this novel anode will pave the way to the development of binder-free anodes in response to the increasing demands for high-power energy storage.