Two synthetic pathways have been elaborated to prepare new series of highly fluorinated sulfamates with excellent yields. Surface tension measurements at the air/water interface showed that these compounds constitute new excellent non-ionic surfactants exhibiting high surface activity in the range of the best non-ionic fluoro surfactants already described in the literature. The most important feature of this work is that, in comparison with the classical non-ionic fluoro surfactants, these sulfamates are easily synthesized in a monodisperse form from classical and relatively non-toxic starting materials. The critical micelle concentration (CMC), the maximum surface excess concentration (Gamma) and the minimum area per molecule (a) have been calculated from the surface tension measurements on surfactant aqueous solutions. Relationships have been established between the length of both the fluorinated tail and hydrocarbon spacer linking the hydrophobic tail to the hydrophilic head, and the interfacial properties. (C) 2008 Elsevier Inc. All rights reserved.