A series of partially fluorinated cationic gemini surfactants and their corresponding monomeric surfactants have been studied by isothermal titration microcalorimetry. The critical micelle concentration (CMC) and enthalpy of micellization (Delta H-mic) were obtained front calorimetric curves. The CMCs of the gemini surfactants are much lower than those of the corresponding monomeric surfactants and decrease with an increase in the number Of fluorine atoms on the hydrophobic chain. The micellization of partially fluorinated cationic gemini surfactants is much more exothermic than that of the corresponding monomeric surfactants. Because of the incompatibility of hydrocarbon spacer and partially fluorinated chains Delta H-mic values of the surfactants with a C-6 spacer are more negative than those of the surfactants with a C-12 spacer. The variations in the architecture of the fluorocarbon chain segments may be the reason of the irregularities in the change of Delta H-mic for the gemini surfactants. Moreover, the contribution of the enthalpy generally increases with an increase in the number of fluorine atoms. (c) 2005 Elsevier Inc. All rights reserved.