AbstractThe first general single‐step route to dendritic or cascade polyaryl ethers analogous to common linear polyaryl ethers is described. The sodium salts of four AB2monomers each containing a single phenolic hydroxyl group and two aryl fluorides activated toward nucleophilic substitution by carbonyl, sulphonyl, or tetrafluorophenyl moieties are shown to polymerize in hot N, N‐dimethylacetamide. The products are high molecular weight polymers (7000