Chlorination is a common practice to prevent biofouling in municipal water supplies, wastewater reuse and seawater desalination. However, polyamide thin-film composite reverse osmosis membranes—the premier technology for desalination and clean-water production—structurally deteriorate when continually exposed to chlorine species. Here, we use layer-by-layer interfacial polymerization of 3,5-dihydroxybenzoic acid with trimesoyl chloride to fabricate a polyester thin-film composite reverse osmosis membrane that is chlorine-resistant in neutral and acidic conditions. Strong steric hindrance and an electron-withdrawing group effectively prevent direct aromatic chlorination, and residual OH groups capped with isophthaloyl dichloride preclude reaction with active chlorine. The poly(isophthalester) membrane exhibits high salt rejection (99.1 ± 0.2%) and water permeability (2.97 ± 0.13 l m−2 h−1 bar−1), even after demonstrating biofouling prevention with chlorine (50 mg l−1 of NaOCl for 15 min). We anticipate that our chlorine-resistant membrane will greatly advance reverse osmosis desalination as a sustainable technology to meet the global challenge of water supply.