Zinc-based aqueous rechargeable batteries have attracted extensive attention due to their low cost, safety, and environmental friendliness. However, dendrite growth and hydrogen evolution of Zn anodes limit their large-scale application. A new strategy to produce a polyacrylamide/reduced graphene oxide (PAM@rGO) molecular nanobrush coating and control Zn electrolyte interface engineering is proposed for use in highly reversible Zn plating/stripping. Hydrogen evolution is inhibited, and Zn deposition is consolidated using the rich zincophilic functional groups of the branched polyacrylamide chain and the high conductivity of rGO. Due to the synergistic effects of corrosion resistance and dendrite-free growth, PAM@rGO/Zn provides prolonged and reversible Zn plating/stripping. Density functional theory (DFT) calculations expand on homogenized nucleation. The PAM@rGO/Zn||activated carbon (AC) capacitor exhibits long cyclic stability, fast ion transfer, and minimal interfacial impedance. This study provides experimental and theoretical bases for the structural design of Zn anode.