New hydrophobically modified pullulans were synthesized in two ways: (i) neutral derivatives (HMPFs) obtained by direct esterification of pullulan with a perfluoroalkyl carboxylic acid (C8F17CH2CH2COOH), and (ii) ionic derivatives (HMCMPs) obtained by amidation of carboxymethylpullulan with two perfluoroalkylamines (C7F15CH2NH2 and C8F17CH2CH2NH2). The molar hydrophobe contents ranged from 1.1 to 4.8% with respect to the anhydroglucose units. Associative properties in aqueous solutions were studied by rheological and size-exclusion chromatography/light-scattering measurements. In dilute solution, the polymers form intermolecular aggregates with a more compact conformation than that of precursors. In semi-dilute solution, the ionic derivatives are more viscosifying than neutral because of. their better solubility. This effect is significant as the alkylperfluorinated chain length increases.