A facile covalent assembly strategy is proposed for the preparation of superhydrophobic COF-stabilized MXene separation membranes. Ultra-high separation fluxes of up to 54 280 L m-2 h-1 and 643 200 L m-2 h-1 bar-1 are obtained for emulsified water-in-oil mixtures by adopting gravity and external pressure, respectively. Moreover, the challenges of easy swelling and oxidation properties of MXene have been effectively overcome via the COF-stabilized mechanism.