Voltammetric thin layer (∼200 nm) ionophore-based polymeric films of defined ion-exchange capacity have recently emerged as a promising approach to acquire multi-ion information about the sample, in analogy to performing multiple potentiometric measurements with individual membranes. They behave under two different regimes that are dependent on the ion concentration. A thin layer control (no mass transport limitation of the polymer film or solution) is identified for ion concentrations of >10 μM, in which case the peak potential serves as the readout signal, in analogy to a potentiometric sensor. On the other hand, ion transfer at lower concentrations is chiefly controlled by diffusional mass transport from the solution to the sensing film, resulting in an increase of peak current with ion concentration. This concentration range is suitable for electrochemical ion transfer stripping analysis. Here, the transition between the two mentioned scenarios is explored experimentally, using a highly silver-selective membrane as a proof-of-concept under different conditions (variation of ion concentration in the sample from 0.1 μM to 1 mM, scan rate from 25 mV s-1 to 200 mV s-1, and angular frequency from 100 rpm to 6400 rpm). Apart from experimental evidence, a numerical simulation is developed that considers an idealized conducting polymer behavior and permits one to predict experimental behavior under diffusion or thin-layer control.