We report on the effect of commercially important polysaccharides (maltodextrins with variable dextrose equivalent (Paselli SA-2, MD-6 and MD-10) on the surface activity at the air-water interface of small-molecule surfactants (sms), possessing different hydrophobic-lipophilic balance ((SSL (Na+), the main component is a sodium salt of stearol-lactoyl lactic acid, and PGE (080), polyglycerol ester of C18 fatty acid), and widely used in food products. A marked change of the surface activity of sms was found in the presence of maltodextrins by tensiometry. The combined data of laser multiangle light scattering and mixing calorimetry have suggested that this result is governed by specific complex formation between maltodextrins and sms in aqueous medium. Measurements have been made of the molar mass, the second virial coefficient and the enthalpy of intermolecular interactions in aqueous solutions. The implication of a degree of polymerization of maltodextrins in this phenomenon was shown. The interrelation between the molecular parameters of the formed complexes and their surface activity at the air-water interface has been revealed and discussed. (C) 2003 Elsevier B.V. All rights reserved.