A multi-block associative polyelectrolyte based on poly(methacrylic acid-ra-styrene) [MAA-S] and poly(octadecyl methacrylate) [ODMA] was synthesized through stepwise nitroxide-mediated solution polymerizations. The obtained polymer has a heptablock copolymer structure, alternating MAA-S as hydrophilic blocks (theoretical degree of polymerization [DPT] of 250), and ODMA as hydrophobic blocks (DPT = 15). Rheological properties, in the linear-response regime, of aqueous solutions (polymer content = 1.5 wt.%) were studied as a function of the amount of blocks on the polymer using steady-shear and creep-compliance experiments. Rheological experiments demonstrate that the viscoelastic behavior of the polymer bearing an ODMA block in terminal position greatly differs from that of the polymer with MAA-S block terminations. The former behaves as a newtonian fluid on a wider range of shear rates than the latter, which exhibit a shear-thinning behavior, even at low shear rates, independently of the molecular weight and number of blocks.