The voltammetric response of a bipolar cell, formed by making electrical connection between two half-cells under overall potentiostatic control, is described. Experimental data obtained with reversible redox couples are compared with numerical simulations of the corresponding two-phase transport problem, where charge transfer may be limited by the transport of either, or both, of the redox-active couples. Preliminary experiments on the extension of the system to more complex electron transfer processes, specifically metal deposition, are also described.