As a key component of batteries, the electrolyte determines the ion transport and interface chemistry of the cathode and anode. In this work, we develop a dual‐network structured hydrogel electrolyte composed of polyacrylamide (PAM), sodium alginate (SA) and potassium iodide (KI) for solid‐state zinc‐air/iodide hybrid batteries. The assembled hybrid battery shows excellent renewability and a long cycling life of 110 h with a high energy efficiency of 80 %. The ion‐crosslinked dual‐network structure endows the material with improved mechanical strength and increased ionic conductivity. More importantly, the introduction of iodine species not only offers more favorable cathodic kinetics of iodide/iodate redox than oxygen electrocatalysis but also regulates the solvation structure of zinc ions to ensure better interface stability. This work provides significant concepts for developing novel solid‐state electrolytes to realize high‐performance energy devices and technologies.