Diaryl ethers containing condensed polycyclic aryl groups were synthesized from arenols in the presence of a catalytic amount of p-chlorobenzenesulfonic acid. Symmetrical binaphthyl, biphenanthryl, and bipyrenyl ethers were obtained in high yields. Unsymmetrical derivatives were also synthesized from 9-phenanthrol and arenols, using combinations of reactive and unreactive substrates.