Uncontrolled dendrite growth, severe parasitic reactions on the Zn metal anode (ZMA), and the dissolution of cathode active materials have significantly limited the development of aqueous zinc ion batteries. Herein, 3-(Cyclohexylamino)-1-propanesulfonic acid (CAPS) featured with zwitterion as a multifunctional additive is introduced into the 2 M ZnSO4 aqueous electrolyte to simultaneously regulate the interfacial chemistry of the Zn anode and the cathode, as well as the solvated structure of Zn2+, thereby improving the interfacial and structural stability of both electrodes. Thereinto, the preferentially adsorbed CAPS zwitterion onto the ZMA surface favors for constructing a cationic protective layer originated from the electrostatic shielding effect of the cationic group (>NH2+), inhibiting the growth of dendrites. Meanwhile, the CAPS zwitterion can self-regulate the bilateral interfacial pH by forming the conjugate acid-base pair, suppressing hydrogen evolution reaction and Zn anode surface corrosion. Additionally, the CAPS zwitterion alters the solvated structure of Zn2+, weakening H2O molecule activity and reducing the dissolution of vanadium element from cathode. Consequently, the Zn||Zn symmetric cells harvest excellent cycling stability (1 mA cm−2, 1 mAh cm−2, 2300 h), and the Zn||Cu asymmetric cells display a high average Coulombic Efficiency of 99.7 % after 1600 cycles in the ZnSO4+CAPS electrolyte.