Fluorescent spectroscopic studies on the complexation of naphthalene-appended amino-beta-cyclodextrins, 1 and 2, with anionic, cationic, and nonionic surfactants have been carried out. In host 1-surfactant system, an excellent fluorescent signal change was observed. On the other hand, host 2 exhibits no photophysical response in the presence of various surfactants. The difference in the properties between 1 and 2 was interpreted by difference in the inclusion depth of the naphthalene units for C the cyclodextrin cavity. The binding abilities and thermodynamic (Delta H degrees, Delta S degrees, and Delta G degrees) quantities of 1-surfactant system have been discussed to characterize structure/enegetics for the complexation process.