The term halogen bonding describes the tendency of halogen atoms to interac
t with lone pair possessing atoms. The binding features and structural prop
erties of halogen bonding are discussed and applied to drive the intermolec
ular self-assembly of hydrocarbons and perfluorocarbons in chemo-, site-, a
nd enantioselective supramolecular synthesis. The halogen bonding is thus a
n effective and reliable tool in crystal engineering at the disposal of the
supramolecular chemist.