AbstractHydrogel electrolytes (HEs), characterized by intrinsic safety, mechanical stability, and biocompatibility, can promote the development of flexible aqueous zinc‐ion batteries (FAZIBs). However, current FAZIB technology is severely restricted by the uncontrollable dendrite growth arising from undesirable reactions between the HEs with sluggish ionic conductivity and Zn metal. To overcome this challenge, this work proposes a molecular engineering strategy, which involves the introduction of oxygen‐rich poly(urea‐urethane) (OR‐PUU) into polyacrylamide (PAM)‐based HEs. The OR‐PUU/PAM HEs facilitate rapid ion transfer through their ionic hopping migration mechanism, resulting in uniform and orderly Zn²⁺ deposition. The abundant polar groups on the OR‐PUU molecules in OR‐PUU/PAM HEs break the inherent H‐bond network, tune the solvation structure of hydrated Zn²⁺, and inhibit the occurrence of side reactions. Moreover, the interaction of hierarchical H‐bonds in the OR‐PUU/PAM HEs endows them with self‐healability, enabling in situ repair of cracks induced by plating/stripping. Consequently, Zn symmetric cells incorporating the novel OR‐PUU/PAM HEs exhibit a long cycling life of 2000 h. The resulting Zn–MnO₂ battery displays a low capacity decay rate of 0.009% over 2000 cycles at 2000 mA g⁻¹. Overall, this work provides valuable insights to facilitate the realization of dendrite‐free Zn‐metal anodes through the molecular engineering of HEs.