Surfactants which contain one or more fluorinated or partially fluorinated hydrophobic groups (fluorinated surfactants or ‘fluorosurfactants’) can show dramatically different properties to those of hydrocarbon surfactants. The special properties of fluorosurfactants, which result from the unique properties of fluorocarbon chains, makes them irreplaceable in a wide range of applications and justifies Kissa’s claim in his 1994 text on the subject that fluorinated surfactants are truly ‘super surfactants’ [1]. Rather than exhaustively review the huge literature on fluorosurfactants, the main aim of this chapter is to give an account of the special surfactant properties of fluorinated surfactants and to relate these properties to the differences in physical properties between fluorocarbon and hydrocarbon chains.