Based on the great advantages of an inner hollow structure and excellent solid counterpart capacity, complex hierarchical structures have been widely used as electrodes for lithium-ion batteries. Herein, hierarchical yolk–shell Cu₂O@CuO-decorated RGO (YSRs) was designed and synthesized via a multi-step approach. Octahedron-like Cu₂O-decorated RGO was firstly produced, in which GO was reduced slightly while cuprous oxide was synthesized. Subsequently, the controlled oxidation of Cu₂O@RGO led to the synthesis of special YSRs, which were composed of a solid Cu₂O core, spur-CuO, CuO shell, and RGO covered. As anode materials, YSRs could provide considerable capacity density. Meanwhile, the void existed between shells and solid active materials retaining the advantages of inner hollow structure. As a result, the unique architecture of the materials renders the composites with enhanced electronic and ionic diffusion kinetics, high specific capacity (~894 mAh g^-1, 0.1C), and an excellent rate capability.