Time-resolved fluorescence quenching studies of nonionic, anionic, and cationic micelles have been performed to compare two surfactant quenchers, a fluorocarbon surfactant quencher, N-(1,1,2,2-tetrahydroperfluorodecanyl)pyridinium chloride (HFDePC) and a hydrocarbon quencher of similar hydrophobicity, C16PC, N-hexadecylpyridinium chloride. The concentration dependence of the apparent aggregation numbers informs on the interaction between the surfactants, which always was repulsive for the fluorocarbon quencher in hydrocarbon micelles, except for the case with a nonionic micelle, where the effectively attractive electrostatic interaction dominated at low ionic strength. The simple theory (Almgren, M.; Hansson, P.; Wang, K. Langmuir 1996, 12, 3855) suggests that the interaction parameter from the slope of the apparent aggregation number versus mole fi action quencher should be the same as the interaction parameter describing the change of the critical micelle concentration with composition according to regular solution theory (Rubingh, D. H. In Solution Chemistry of Surfactants; Mittal, K. L., Ed.; Plenum Press : New York, 1979; Vol. 1, p 337). The results show that it is not so; not even the sign of the interaction parameter is always the same. The reasons for the difference are discussed. For the weight average aggregation number, obtained by extrapolation to zero quencher concentration, the two quenchers gave results within about 10% for a given surfactant; the values with the fluorocarbon quencher seemed to be systematically lower, as if the aromatic probe strongly avoided micelles containing fluorocarbon quenchers. From solubility studies, pyrene was found to prefer a C(16)TAC micelle over a HFDePC micelle by a factor of 60. The preference of pyrene for micelles without fluorocarbon surfactants was utilized to show the demixing into fluorocarbon-rich and hydrocarbon-rich micelles in a mixture of lithium perfluorononanoate and lithium dodecyl sulfate and in cetyltrimethylammonium chloride and HFDePC.