The large-scale application of aromatic polyamide (PA) thin-film composite (TFC) membranes for reverse osmosis has provided an effective way to address worldwide water scarcity. However, the water permeability and salt rejection capabilities of the PA membrane remain limited. In this work, cyclic micropores based on crown ether were introduced into the PA layer using a layer-by-layer interfacial polymerization (LbL-IP) method. After interfacial polymerization between m-phenylenediamine (MPD) and trimesoyl chloride (TMC), the di(aminobenzo)-18-crown-6 (DAB18C6) solution in methanol was poured on the membrane to react with the residual TMC. The cyclic micropores of DAB18C6 provided the membrane with rapid water transport channels and improved ion rejection due to its hydrophilicity and size sieving effect. The membranes were characterized by FTIR, XPS, SEM, and AFM. Compared to unmodified membranes, the water contact angle decreased from 54.1° to 31.6° indicating better hydrophilicity. Moreover, the crown ether-modified membrane exhibited both higher permeability and enhanced rejection performance. The permeability of the crown ether-modified membrane was more than ten times higher than unmodified membranes with a rejection above 95% for Na2SO4, MgSO4, MgCl2, and NaCl solution. These results highlight the potential of this straightforward surface grafting strategy and the modified membranes for advanced water treatment technologies, particularly in addressing seawater desalination challenges.