It is generally considered that complexes of cyclodextrins (CDs) with ordinary surfactants are not surface-active in water. In this work, aqueous mixtures of alpha-CD, octyltriethylammonium bromide (OTEAB), and sodium perfluorooctanoate (SPFO) were studied by surface tension measurements. Comparison of the experimental results and the simulated ones in the premicellar region showed that the ability of the alpha-CD/OTEAB complexes to participate in the surface-adsorbed layer was dependent on the overall net charge of the surfactants: for the excess-SPFO system, the alpha-CD/OTEAB complexes did show a significant contribution to the surface activity of the mixture, but in the system with excess OTEAB, the alpha-CD/OTEAB complexes were not observed to influence the surface-adsorbed layer. We speculated that the surface-adsorbed layer in the premicellar region might also prefer an electroneutral state, as those cationic-anionic micelles did, and that the alpha-CD/OTEAB complexes were driven to the surface by electrostatic attractions from the excess oppositely charged SPFO. The calculated results for the surface area per molecule adsorbed at the air-water interface also supported our conclusion.