In this work we studied and compared the physicochemical properties of the catanionic mixtures cetyltrimethyl-ammonium bromide-sodium dodecanoate, cetyltrimethyl-ammonium bromide-sodium perfluorodacanoate, octyltrimethylammonium bromide-sodium perfluorodacanoate and cetyltrimethyl-ammonium bromide-sodium octanoate by a combination of theological, transmission electron microscopy (TEM) and polarized optical microscopy measurements. The binary mixtures of the surfactants have been analyzed at different mixed ratios and total concentration of the mixture. Mixtures containing a perfluorinated surfactant are able to form lamellar liquid crystals and stable spontaneous vesicles. Meanwhile, system containing just hydrogenated surfactants form hexagonal phases or they are arranged in elongated aggregates. (C) 2009 Elsevier Inc. All rights reserved.