Flexible all-solid-state zinc–air batteries (AZABs) paired with flexible perovskite solar cell successfully produce photo-rechargeable zinc–air batteries (PAZABs) that can directly convert solar energy into electrical energy and store it in real-time. The open-circuit voltage (V_OC) of a AZAB directly influences the energy density of PAZABs. However, increasing the V_OC remains a significant challenge. In this work, we designed and synthesized a functional gel electrolyte with multiple ion channels, achieving an impressive V_OC of 1.55 V for the AZABs. This polymer structure enhances OH⁻ transport by increasing the number of N⁺ sites, providing abundant multi-ionic transport channels, and accelerating the storage rate of photogenerated charges. Additionally, the synergistic interaction between N⁺ and –COO⁻ increases the binding energy with H₂O, elevates the electron cloud density at the Zn anode interface, suppresses the formation of ZnO, and improves the cycling stability of the AZABs. The flexible AZABs exhibit a high discharge capacity of 740 mAh·g⁻¹. When coupled with flexible perovskite solar cell, the PAZABs achieved impressive 16.5% overall conversion efficiency, setting a new benchmark among peers.