Abstract The inherent safety, low cost, and eco‐friendliness of aqueous zinc‐metal batteries (AZMBs) make them prime contenders for large‐scale energy storage. Their development is, nevertheless, hindered by serious side reactions and uneven zinc deposition, which degrade Coulombic efficiency (CE) and cycle life. Herein, a bio‐inspired buffer engineering strategy is reported utilizing TAPSO, a multi‐functional biological buffer. TAPSO orchestrates zinc‐ion coordination chemistry to attenuate water reactivity, significantly suppressing hydrogen evolution and corrosion. Moreover, it constructs a protective anode‐electrolyte interphase while reorganizing hydrogen‐bond networks, which jointly inhibit dendritic growth and deleterious byproduct formation. This approach enables an unprecedented cycling lifespan of over 2 200 h for Zn||Zn symmetric cells and a high average CE of 99.72% over 1 200 cycles for Zn||Cu half‐cells. Remarkably, Zn||NH 4 V 4 O 10 full cells retain 94.1% capacity after 2 000 cycles. The practicality of this strategy is further demonstrated by a pouch cell that stably delivers nearly 40 mAh for 50 cycles. This study establishes a transformative paradigm for enabling advanced AZMBs in sustainable energy storage systems.