Aggregation properties of sodium hyaluronate (NaHA) with alkanediyl-alpha,omega-bis(dimethylalkylammonium bromide) surfactants (referred to as dimeric surfactants) in aqueous sodium chloride solutions have been studied as a function of surfactant chemical structure. Surface tension measurements indicate the unusual parabolic dependence of surface tension vs log surfactant concentration with a surface tension minimum at concentration c(min). The increase of surface tension above c(min) may be related to the formation of clusters consisting of NaHA chain and dimeric surfactants at the air-water interface and in the bulk. From light scattering measurements, molecular weight, hydrodynamic radius, and second virial coefficient have been calculated. The simple calculation of the ratio of positive charge of dimeric surfactant unit per one negatively charged hyaluronate disaccharidic unit in NaHA-surfactant complex reveals that there is a slight excess of positive surfactant charges per one negatively charged disaccharidic unit in the region around c(min) and the NaHA-surfactant complex is not far from electroneutrality. The nonlinear behavior of viscosity vs surfactant concentration in the NaHA-dimeric surfactant system depends on surfactant chemical structure. The behavior is concerned with the size increase due to complex growth and with the size shrinkage above c(min). A model describing the behavior of NaHA-surfactant complex in the bulk and at the interface is suggested. Copyright 2000 Academic Press.