The Zn-Ag and Zn-Ag/air hybrid batteries are challenged by the low conductivity and capacity of Ag electrode materials. How to further optimize and tune the surface electronic structure of Ag nanomaterials has become an important topic in the improvement of Ag electrode materials. Herein, the silver nanobelts (Ag NBs) materials were prepared by a fast and simple redox replacement reaction. The special nanobelts structure, with the key surface features of the gully-like morphology, raised Ag mounds and superlattice fringes, are beneficial to tune the surface electron structure and thereby increase the conductivity and electrochemical performance of Ag NBs. As a consequence, the assembled Zn-Ag battery exhibits favorable electrochemical performance in view of the specific capacity of 380.9 mAh gAg−1. In addition, the hybrid Zn-Ag/air battery shows two-step voltage plateaus of 1.83 and 1.55 V in the Zn-Ag reaction, as well as a voltage plateau of 1.23 V corresponding to the Zn-air reaction. The hybrid battery maintains a high energy efficiency of 76.9% and high rate capabilities, demonstrating an excellent energy-saving feature of this battery. The insights gained from this work may be beneficial for designing the highly-efficient Ag catalysts for electrochemical energy storage.