Silicone surfactants containing different pendant hydrophilic groups such as diethanol tertiary amine (SHE, nonionic), diethanol methyl quaternary amine (cationic) and triethyl quaternary amine (cationic) have been synthesized and characterized by H-1 and C-13 NMR and gel permeation chromatography. The solution behavior of these novel surfactants has also been investigated by surface tension measurement and a fluorescence method. It has been observed that the surface tension of these surfactants decreases as a function of time at a very low polymer concentration (1 x 10(-4) wt%). At higher concentration (0.1 wt%), the equilibrium surface tensions reached very low values compared to that of typical polymer surfactants, for example, poly(ethylene oxide-propylene oxide) block copolymer (EPE0.8). In addition, the low I-1/I-3 values of these silicone surfactants indicate the formation of polymer aggregates in aqueous solution, and an extremely low I-1/I-3 value of SHE (1.06) compared to other polymeric surfactants (EPE0.8) and conventional surfactants [poly(ethylene glycol n-nonyl phenyl ethers), cetyltrimethylammonium bromide, and sodium dodecyl sulfate] indicates its stronger hydrophobicity.