Aqueous AgO-Al batteries are promising systems due to their ultrahigh specific capacity, energy density, and stable output voltage. However, they still suffer from the low utilization and sluggish kinetics of the cathode. In this study, the binder-free AgO/AgNPs composites were synthesized in-situ using a simple electrodeposition method. Due to the excellent conductivity and rich mesoporous structure of AgO/AgNPs materials, the electron and ion transfer kinetics were enhanced, thereby improving the charge storage performance of the electrode. As expected, the AgO-Al battery with the optimized AgO/AgNPs composite cathode demonstrated excellent rate performance, achieving a high discharge capacity of 325.1 mAh g−1, and a stable operating voltage platform of 1.55 V at the current density of 1000 mA cm−2. The maximum energy and power density were 687 Wh kg−1 and 6.2 kW kg−1, respectively. This work presents an effective strategy for designing high-performance AgO electrode materials for AgO-Al batteries.