Interactions between sodium poly(acrylate) (NaPAA) and dodecyltrimethyl/ethyl/propyl/butylammonium bromide (C12NM, C12NE, C12NP, and C12NB) were studied. Variation of the physicochemical properties of the surfactants and polyelectrolyte-surfactant mixtures, such as critical micelle concentration (cmc), critical aggregation concentration (cac), micellar micropolarity, aggregation number, and pyrene lifetime, were determined by steady-state and time-resolved fluorescence methods. It is shown that the surfactant head group size has a striking effect on the interaction between surfactant and polyelectrolyte. The interaction is weakened gradually when the surfactant head group is increased from trimethyl to tripropyl, which might be owing to the increase of the steric hindrance between the polyelectrolyte chain and micellar surface. But when the head group is tributyl, the interaction is enhanced and stronger than that between C12NP and NaPAA. This might be explained by the self-association of the C12NB head groups. (C) 2004 Elsevier Inc. All rights reserved.