The apparent degradation of alkaline fuel cells performance at reduced relative humidity (RH) drives the interest in further improving anion exchange membranes (AEMs) functionalities and/or developing alternative AEMs. Herein, we report an AEM with urea-based structure that exhibits excellent low humidity performance. Microstructure analysis and molecular dynamics simulation show that hydrogen bonding between urea-based structures enhances the self-assembly ability of quaternary ammoniums groups and expanded OH − conduction pathway. Besides, the hydrogen bond network formed by urea-urea group and urea-water group endows the AEMs with excellent water retention ability, thereby decreasing the dependence of OH − conduction on RH. The resultant AEM shows outstanding fuel cell power density (210 mW cm −2 ) under special operating conditions like 40 °C and 50% RH, which exhibits 2.5 times better than hydrogen bonding-free AEM. This work simulates the real working state of the fuel cells and provides significant guidance for rapid start-up in anion exchange membrane fuel cells (AEMFCs). • •Intra-molecular hydrogen-bonding interactions was proposed for enhancing the performance of fuel cells under special operating conditions like 40 °C and 50% RH. • •Hydrogen-bonding interactions promote the rapid conduction of OH − . • •Hydrogen-bonding network endows AEMs with excellent water retention ability.