The present article focuses on the comparative study of physicochemical properties of two ionic pullulan derivatives modified by 10 or 35 C-8 chains per 100 anhydroglucose units, named CMP10C8 and CMP35C8, respectively. In aqueous solutions, these derivatives exhibited an associative behavior as evidenced by pyrene fluorescence spectroscopy. This phenomenon, which stems from intra- and/or intermolecular interactions between the hydrophobic groups grafted on the polymer backbone, results in the formation of more or less condensed aggregates depending on the C-8 ratio and the ionic strength of the media. The hydrophobically modified pullulans also displayed surface properties. Their adsorption at the air-solution interface was assessed from surface tension measurements. The results showed that both hydrophobized polymers adsorb in a coil conformation occupying a large interfacial molecular area. The comparison of these molecular areas indicated that CMP35C8 adopts a more shrunken conformation at the interface than CMP10C8, due to stronger intramolecular interactions. The stability of the adsorbed monolayer under bulk dilution was investigated by ellipsometric measurements. Whereas bulk dilution had no effect on the stability of the adsorbed CMP35C8 film, it provoked significant changes in the adsorbed CMP10C8 monolayer. The stability of the CMP35C8 monolayers was attributed to the existence of intermolecular associations between the adsorbed coils. (C) 2004 Elsevier Inc. All rights reserved.