AbstractGraphene oxide (GO) membranes have shown great prospects as the next‐generation membranes to tackle many challenging separation issues. However, the employment of GO membranes remains difficult for the precise separation of molecules with strong coupling effect and small size discrepancy such as water–ethanol. Herein, a new strategy of constructing exclusive and fast water channels in GO membrane was proposed to achieve high‐performance water–ethanol separation via the synergy between zwitterion‐functionalized GO and hydrophilic polyelectrolyte. The as‐formed ordered and stable channels possess high‐density ionic hydrophilic groups, which benefit from inhibiting the strong coupling between water and ethanol, facilitating the fast permeation of water molecules while suppressing ethanol molecules. As a result, the ultrathin GO‐based membrane acquires exceptionally high separation performance with a flux of 3.23 kg/m2 h and water–ethanol separation factor of 2,248 when separating water–ethanol (10 wt%/90 wt%) mixture at 343 K. This work paves a feasible way to construct 2D channels for the high‐efficiency separation of strong‐coupling mixtures.