In 1967, Charles Pedersen, who was a chemist working at DuPont, discovered a simple method of synthesizing a crown ether when he was trying to prepare a complexing agent for divalent cations. His strategy entailed linking two catecholate groups through one hydroxyl on each molecule. This linking defines a polydentate ligand that could partially envelop the cation and, by ionization of the phenolic hydroxyls, neutralize the bound dication. He was surprised to isolate a by-product that strongly complexed potassium cations. Citing earlier work on the dissolution of potassium in 16-crown-4, he realized that the cyclic polyethers represented a new class of complexing agents that were capable of binding alkali metal cations. He proceeded to report systematic studies of the synthesis and binding properties of crown ethers in a seminal series of papers. The fields of organic synthesis, phase transfer catalysts, and other emerging disciplines benefited from the discovery of crown ethers.  Pedersen particularly popularized the dibenzo crown ethers.
Pedersen shared the 1987 Nobel Prize in Chemistry for the discovery of the synthetic routes to, and binding properties of, crown ethers.