Self-assembly in aqueous solutions of an amphiphilic comblike polyelectrolyte (80C12) that consists of a polystyrene (PS) backbone onto which quaternary ammonium pendant moieties have been grafted has been investigated by light scattering and cryo-transmission electron microscopy measurements in the presence of KCl and methylviologen dication (MV2+) under conditions mimicking those for electrochemical measurements. Polymer chains self-assemble within branched cylindrical micelles that display viscoelastic properties, characterized by a relaxation time of 4 s. To tune this time, 80C12 was mixed with a polyoxyethylene nonionic surfactant (Brij C12E10). Relatively increasing the amount of the latter leads to a decrease in the relaxation time of the 80C12 solution. Correlatively, electrochemical experiments with a rotating disk electrode show a transition of the mass transport rate, which deviates from the classical Newtonian behavior in the same velocity domain. This result generalizes what has been already observed with solutions of linear polymers of high molecular weight and wormlike micelles based on surfactants subjected to elongational deformations. Moreover, the critical times derived from rheological and electrochemical experiments display the same trend.