EDOT 𝑛+ oligomers are rapidly generated in the organic diffuse layer at positive applied Δ o w 𝜙 during the forward scan in Fig. . These oligomers may undergo a homogenous comproportionation reaction in the organic diffuse layer with neutral EDOT monomers and become partially reduced to EDOT (𝑛-1)+ . Then, upon reversing the cycle direction, the EDOT (𝑛-1)+ species are re-oxidised to EDOT 𝑛+ by IET with Ce 4+ (leading to the CV trace crossover). In line with the descriptions by Heinze et al. of electropolymerisation at solid electrode|electrolyte interfaces, this interpretation of a nucleation loop prerequisites that (i) the standard redox potentials of the redox active oligomer (EDOT (𝑛-1)+ ) and EDOT monomer are close, with that of the monomer being more positive than that of the oligomer, and (ii) the rate of the IET reaction between Ce 4+ and the EDOT monomer at the bare L|L interface must be sluggish. The latter slows the depletion of neutral EDOT in the organic diffuse layer, thereby enabling the homogeneous oxidation of EDOT via a comproportionation reaction to proceed (or compete). This autocatalytic mechanism thereby considerably facilitates the starting oxidation of neutral EDOT, with dramatic changes in the CVs (associated with oligomer adsorption and PEDOT thin film formation) observed in the cycles immediately following the cycle containing the nucleation loop.