We report synthesis of surface-active quaternary amino polyfluorosiloxanes. Hydrosilation of silanic hydrogen containing polyfluorosiloxanes with olefinic epoxides, in the presence of a platinum-divinyltetramethyldisiloxane complex gave epoxy polyfluorosiloxanes. These, on further reaction with various amines followed by quaternization, gave quaternary amino polyfluorosiloxanes. The quaternary amino polyfluorosiloxanes reduce surface tension of water to 25 mN/m(2) at a 25-millimolar concentration.