Conducting polymers (CPs) constitute a class of materials with unique mechanical, optoelectronic, redox, and photovoltaic properties. CPs find widespread applications in bioelectronic (e.g., neural interfaces, organic electrochemical transistors, electronic skin), energy harvesting and storage (e.g., batteries, supercapacitors, organic solar cells), electrochromic, (bio)sensor, drug delivery, and soft robotic technology. In a majority of these technologies, the CPs are incorporated as two-dimensional (2D) thin films to take advantage of their light, flexible, and transparent nature. Liquid|liquid (L|L) interfaces provide a simple, template-free, and cost-effective route to 2D thin film synthesis. Certain L|L interfaces, known as interfaces between two immiscible electrolyte solutions (ITIES), are polarisable and enable electrochemical control over the interfacial synthesis of thin films. The foundational work on electrosynthesis of CPs, e.g., poly(thiophene), poly(terthiophene), and various derivatives of poly(pyrrole), and their nanocomposites with metallic nanoparticles or carbon nanotubes at polarisable L|L interfaces was carried out by the groups of Cunnane, Mareček, and Dryfe. CP nanocomposites with metallic nanoparticles were also electrosynthesised at a miniaturised aqueous|1,2-dichloroethane interface by Stockmann's group and a miniaturised aqueous|hydrophobic ionic liquid interface by Nishi et al. The basic concept is that, through polarisation of the L|L interface, electrochemical control over the kinetics of interfacial electron transfer (IET) between aqueous soluble oxidant and organic soluble monomer redox couples is achievable. Recently, we reported an advance in the use of electrosynthesis at a polarisable aqueous|α,α,α-trifluorotoluene (TFT) interface to prepare freestanding, additive-free, reproducible, easily transferrable, scalable, and biocompatible poly (3,4-ethylenedioxythiophene) (PEDOT) thin films in a single-step at ambient conditions using aqueous Ce 4+ and organic soluble EDOT. Our study of the electrosynthesis of PEDOT thin films by double potential step chronoamperometry (DPSCA) at a polarisable aqueous|TFT interface demonstrated that the IET step between Ce 4+ and EDOT to form cationic EDOT oligomers occurs at a positive, externally-applied interfacial Galvani potential difference ∆ o w 𝜙, while interfacial adsorption of the oligomers occurs at a more negative ∆ o w 𝜙. As a consequence, potentiodynamic or multistep potentiostatic are favoured over single-step potentiostatic electrochemical techniques.