The critical micelle concentrations (CMCs) of 1,1,2,2-tetrahydroperfluoroalkylpyridinium chloride have been determined by measurements of surface tension and electrical conductivity, etc. The CMCs of perfluorinated surfactants were only about 0.02 times that of hydrocarbon one with the same carbon number. Aqueous solutions of fluorocarbon surfactants gave low surface tensions in comparison with those of hydrocarbon surfactants. The area per surfactant molecule at the air-water interface decreased with increasing length of the fluorocarbon chain. Electromotive force measurements were made with chloride-responsive electrodes on surfactants solutions. The micelle ionization degrees decreased with increasing length of the alkyl chain. The group contribution method simulated the mixture CMCs of binary surfactants with various alkyl chain lengths. The group contribution method proved to be very useful to predict not only the mixture CMCs but also the demixing regions of binary mixtures having great differences in CMC.