PEDOT thin film at the aqueous|TFT interface. The adsorbed EDOT oligomers provide abundant, electrically conductive catalytic sites to catalyse the IET reaction at a much lower overpotential than at a bare L|L interface, as depicted in Fig. . Experimentally a lower overpotential is recorded by the 7 th cycle, with the current onset shifting from ca. +0.3 V for the 3 rd and 4 th cycles (labelled α) to ca. +0.2 V for the 7 th cycle (labelled α*), see Fig. . At an applied Δ o w 𝜙 ≥ +0.2 V, a huge excess of Ce 4+ oxidises the aqueous side of the adsorbed EDOT oligomers, increasing the number of holes within the oligomer chain (decreasing the EDOT oligomers band gap) and thereby decreasing the overpotential needed to oxidise an EDOT monomer on the organic side. Thus, during a CV cycle, the driving force experienced by the adsorbed EDOT oligomers to accelerate IET via this bipolar-like mechanism constantly varies as the interfacial concentration of Ce 4+ and adsorbed electroactive EDOT oligomers varies, being maximal at an applied Δ o w 𝜙 ≥ +0.2 V. The terminology "bipolar-like" is used as a typical bipolar electrode enables electrocatalysis via modulation of their metallic Fermi level, whereas PEDOT has a band gap and does not enable electrocatalysis in such a manner.