Intercalation of seven types of cationic surfactants, including polyfluorinated surfactants, into a cation-exchangeable clay mineral, saponite, was investigated. All of the surfactants were found to intercalate in amounts exceeding the cation exchange capacity (CEC). This tendency was more evident in the cases of the polyfluorinated surfactants, ((((perfluoroalkanoyl)amino)ethyl)hexadecyl)dimethylammonium bromide (CnF-S, where n indicates the number of carbons in the perfluoroalkyl group, F denotes a fluorinated surfactant, and S denotes a surfactant having a single, long alkyl chain); C3F-S exhibited intercalation up to 4.4 times CEC as a saturated adsorption limit. The saponite interlayer distance increased upon surfactant intercalation and reached a constant value at intercalation levels exceeding CEC. The occupied areas for each surfactant molecule decreased in the order C1F-S > C2F-S > C3F-S among the polyfluorinated surfactants. All of the experimental results, including the saturated intercalation levels, the occupied areas, the interlayer distances, and the DSC measurements, suggest that CnF-S intercalated in saponite forms a rigidly packed bilayer structure in which the long alkyl chains tilt at an angle of ca. 35degrees with respect to the clay surface. The microscopic structure of the hybrid compounds is discussed.