and 2-(dibenzyl-4-yl)-7-benzylindole (DBBI) under conditions for potentiodynamic electrochemical polymerization (0.3-0.9 V vs. Ag/Ag + in acetonitrile) underwent dimerization reactions as was shown by simulation of the potentiodynamic cycles. But DBBI alone polymerized (and only on Au), obviously because of its free N and C(3) positions. This conducting polymer could be technically interesting, because it does not show redox activities in the potential range 0.0-1.1 V vs. the Ag/AgCl electrode. Keywords: indoles, electropolymerization, cyclic voltammetry, role of substrate in polymeri-zation, simulation of CV.Indole and some of its derivatives can be polymerized electrochemically. But up to now only a few applications are known, for example, electrodes sensitive to glucose with composite coatings of polyindole and glucose oxidase [1] or to cytochrome C with coatings of 5-carboxyindole [2].The structure and polymerization mechanism of polyindole (PI) and of its derivatives is controversial [3-7], and even some experimental results seem to be contradictory. It is generally accepted that oxidation generates the indolyl radical cation, which can be deprotonated. MO calculations [6] showed that the unpaired electron and the positive charge are delocalized over the whole indole ring and that structures preserving the aromatic ring should be preferred. The high spin densities at N and C(3) positions seem to present themselves for binding.Investigations of methylindoles indicate that 3-methylsubstituted indoles do not polymerize [8,9]. In [10,11] there was reported polymerization of some methylindoles with free C(3) position, whereas other groups could only detect dimerization and trimerization [8,9] and assumed that methyl groups in the pyrrole ring were N H DBBI 1 2 3 4 5 6 7 __________________________________________________________________________________________ 1 FR 8.13. Physical