Rheological and photophysical data are presented for a hydrophobically modified alkali-soluble copolymer, of a constitution similar to materials currently employed as rheology modifiers in water-borne coatings. The copolymer comprises a polyelectrolyte backbone bearing ethoxylate side chains capped with complex alkylaryl groups of a high molar volume. In aqueous alkaline media, the hydrophobes associate dynamically, the topology of the network so formed being dependent on the polymer concentration. Photophysical studies, employing pyrene as a hydrophobic fluorescent probe, indicate the presence of hydrophobic associations. At concentrations below the coil overlap concentration,c*, these associations are predominantly intramolecular. At higher polymer concentrations, intermolecular interactions become more probable. This change in network topology is in qualitative agreement with previous theoretical considerations of associative polymer systems and is reflected in an unusually high concentration dependence of the zero shear viscosity, withη0∼c8. Evidence for shear-induced structuring in steady shear, large amplitude oscillatory shear, and parallel superposed steady and dynamic shear is presented. Such structuring is more pronounced at lower polymer concentrations, consistent with the formation of intermolecular associations at the expense of intramolecular. In contrast to the simple linear telechelic associative polymers considered in a number of previous studies, the network dynamics of the polymer are no longer represented by a single characteristic time. This deviation from a classical Maxwellian response in oscillatory shear is interpreted as a broadening of the relaxation spectrum, arising from the coexistence of both hydrophobic associations and topological entanglements. Mechanistically, stress relaxation is better envisaged in terms of “hindered reptation” [Liebler et al. (1991)] of the chains, rather than Rouse-like behavior moderated purely by the hydrophobe disengagement rate [Annable et al. (1993)].