Abstract
The practical application of aqueous zinc‐ion batteries (AZIBs) is severely limited by water‐induced issues, such as hydrogen evolution reaction, Zn metal corrosion, and cathode dissolution. To simultaneously stabilize the Zn anode and the NaV
3
O
8
(NVO) cathode, we propose a synergistic strategy based on mixed organic phosphate additives, which integrates triethyl phosphate (TEP) for bulk modulation and tris(2,2,2‐trifluoroethyl) phosphate (TFEP) for interfacial regulation. Experimental and computational investigations reveal that the TEP molecules actively participate in the Zn
2+
solvation sheath and disrupt the hydrogen‐bonding network of water. Meanwhile, the TFEP molecules preferentially adsorb onto the electrode surface and undergo reductive decomposition to construct a robust composite solid electrolyte interphase (SEI). The SEI, consisting of an inorganic‐rich inner layer and an organic‐rich outer layer, physically isolates the anode from active water and suppresses dendrite growth. Furthermore, the adsorbed TFEP contributes to the formation of a cathode electrolyte interphase (CEI) at the NVO cathode. Consequently, Zn||Zn symmetric cells achieve an extended cycling lifespan over 550 h at 10 mA cm
−2
and 10 mAh cm
−2
, and Zn||NVO full cells exhibit excellent cycling stability with 92.6 % capacity retention after 500 cycles at 1 A g
−1
. This work provides a synergistic pathway for designing highly stable AZIBs.