A new family of nonionic and cationic amino-hydroxy functional siloxanes have been prepared and characterized. The surface-active properties of such siloxanes can be tailored, enabling their use as a new generation of surfactants. Three siloxane polymers having the empirical formula of Me3SiO-(SiMe2O)x(SiMeHO)ySiMe3, where (1) x = 0, y = 0, i.e., Me2HSiOSiHMe2; (2) x = 0, y = 33; and (3) x = 150, y = 23, were hydrosilylated with allyl glycidyl ether to form epoxysiloxanes in high yields. Various amines react with these epoxysiloxanes to give nonionic aminohydroxysiloxanes also in good yield. Cationic species are obtained upon protonation of the amino nitrogen on the nonionic siloxane side chain, with hydrogen bromide solution. Characterization of all surfactants by FT-IR and NMR spectroscopy is reported. In addition, two-dimensional NMR, studies could accurately elucidate the structure of the organic side groups present.