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The thin-film composite (TFC) nanofiltration (NF) membrane is a very important method in solving the water crisis. However, the fabrication and industrialization of high-performance NF membranes still remains challenging. In this work, zwitterionic NF membranes via microwave-assisted grafting of betaine was first proposed. The resulting polyamide layer showed leaflike nanostructures after modification. Because of the enlarged permeation area and enhanced hydrophilicity derived from the unique leaflike structure, the optimal membrane permeability reached 40.8 L m -1 h -1 bar -1 . This water permeance was 2.2 times as high as the original polypiperazine-amide membrane, with a Na 2 SO 4 rejection maintained at 97.0%. More importantly, the membrane demonstrated excellent selectivity to monovalent and divalent anions. This zwitterionic membrane fabricated by microwave-assisted grafting of betaine provides new insight for industrial scalable NF membranes with great potentials.