Lipophilic background electrolytes consisting of a lipophilic cation and a lipophilic anion, such as tetradodecylammonium tetrakis(4-chlorophenyl) borate (ETH 500), or bis(triphenylphosphoranylidene) ammonium tetrakis[3,5bis(trifluoromethyl) phenyl] borate (BTPPATFPB) are incorporated into the membranes of ion-selective electrodes (ISEs) to improve the detection limit and selectivity of the electrodes and decrease the resistance of the sensing membrane. In this work, spectroelectrochemical microscopy (SpECM) is used in conjunction with chronopotentiometry to quantify the effects of a lipophilic background electrolyte on the concentration profiles induced inside current-polarized membranes and on the measured voltage transients in chronopotentiometric experiments. In agreement with the theoretical model, the lipophilic background electrolyte incorporated into o-NPOE or DOS plasticized membranes decreases the membrane resistance and thus the contribution of migration in the overall transport across ion-selective membranes. Consequently, it has a significant influence on the changing concentration profiles of the ion-ionophore complex during chronopotentiometric experiments.