Aqueous Zn-ion batteries (ZIBs) are considered as a potential large-scale renewable energy storage system. Herein, Cu ion implantation is used to improve the electrochemical performance of δ-MnO2, resulting in a mixed layer-tunnel material δ-MnO2 ([email protected]δ-MnO2) with high capacity, excellent cycle performance, and rate performance as cathode for aqueous ZIBs. The as-obtained [email protected]δ-MnO2 cathode shows a high specific capacity of 470 mAh g−1 at 0.1 A g−1 and maintains a higher specific capacity during long-term cycles of up to 300 times. Meanwhile, the first-principles theoretical simulations suggest the easier migration of Zn2+ and more Zn2+ adsorption on [email protected]δ-MnO2 cathode. The theoretical and experimental results show that Cu ion implantation may be an effective strategy to improve the device performance of the Mn-based layer-tunnel hybrid cathode.