The perfluoroalkylthio amidoalkyl amine or ammonium compounds having the structures ##STR1## where R.sub.f is a perfluoroalkyl, R.sub.1 is alkylene or alkylene oxy or amino alkylene, R.sub.2 is hydrogen or alkyl, R.sub.3 and R.sub.4 are independently alkyl or together form a heterocyclic ring, R.sub.5 is hydrogen or alkyl, R.sub.6 is hydrogen, oxide, alkyl or substituted alkyl, E is alkylene or polyoxyalkylene, X is an anion, y is 1 or 2 and z is 0 or 1, which can be prepared by the base-catalyzed addition of a perfluoroalkylthiol to an .alpha.,.beta.-unsaturated amide. These compounds are useful as surfactants.