the synthesis of unsymmetrical polyfluoroaryl ethers via selective C4–F bond cleavage of pentafluorobenzene is reported. The reaction could proceed smoothly without the requirement of additional metals or ligands, and afford a series of the corresponding products in good to high yields. A wide variety of substituted phenols and alcohols provided 1,2,4,5-tetrafluoropheny ether derivatives in regioselective