An inverse, free-radical emulsion polymerization technique was designed for the preparation of copolymers of acrylamide and sodium acrylate modified with low amounts (<0.5 mol %) of a series of amphiphilic comonomers, the isooctylphenoxy-poly(oxyethylene)(n) metbacrylates (1 less than or equal to n less than or equal to 12). The products of the reaction were hydrophobically modified water-soluble polymers (HMWSPs) of high molecular weight encapsulated within water droplets dispersed in an organic medium. Kinetic studies showed that the full-conversion samples were rather homogeneous in composition because of the specificity of the process. A mechanistic scheme is proposed that accounts for the incorporation level of the amphiphilic comonomer as a function of its hydrophile-lipophile balance and the nature of the redox initiator (hydrophilic or lipophilic). The rheological properties of the HMWSPs in aqueous solutions were investigated as a function of the comonomer content and the nature of the initiator with steady-flow experiments, The thickening properties were directly correlated to the conditions of synthesis and were optimal when the initiator and the amphiphilic comonomer were located in two distinct phases. A maximum in viscosity was observed for a hydrophobe content of about 0.3 mol %. An examination of the viscosity as a function of the shear rate and time showed that these solutions had all the characteristics of associating polymers. The complex rheological behavior was the result of the balance between interchain and intrachain hydrophobic liaisons and the kinetics of disorganization and reorganization of the network structure.