Water-soluble associative polyelectrolytes of methacrylic acid [MAA] and ethyl acrylate [EA] (1:1 molar ratio), hydrophobically modified with small amounts of stearyl metacrylate [MM18], were synthesized by means of solution polymerization. Polyelectrolytes with two different molecular structures: multisticker, with hydrophobic groups randomly distributed along the hydrophilic chain and combined, with the hydrophobic groups along the chain and as terminal groups of the backbone, were obtained. Steady shear behavior and linear viscoelastic properties were studied as a function of polymer microstructure and hydrophobic group concentrations on salt-free aqueous solution using a cone-and-plate rheometer. Concentration regimes were obtained for each synthetized polymer. Viscoelastic study shows that the maximum thickening effect corresponds to the combined structure followed by multisticker structure. These polyelectrolytes exhibit high thickening power on aqueous solutions due to the synergy between the hydrophobic attractive interactions and coil expansion phenomena.