Poly(3,6-N-vinylcarbazole) films were prepared by electrochemical oxidation of N-vinylcarbazole on a Pt electrode using acetonitrile as solvent and tetraethylammonium tetrafluoroborate as electrolyte. The electrosynthesis was carried out by electrical potential cycling in the presence of two different bases: tetraethylammonium benzoate (Bz(-)) and tetraethylammonium phthalate (Ph-). These salts were expected to modify the acidity level of the electrolyte since they can act as scavengers for the protons released during the polymerization, when the reaction takes place in the carbazole unit. Products were characterized by cyclic voltammetry, scanning electron microscopy, FTIR spectroscopy, thermogravimetric analysis, differential scanning calorimetry, absorption spectroscopy and four-probe electrical conductivity measurements. Both bases influenced significantly the chemical structure and morphology of the deposited materials. The presence of Ph- in the electrolyte decreases the cross-linking of the electro-deposited polymer, leading to a poly(3,6-N-vinylcarbazole) bearing a more uniform morphology, higher thermal stability and electrical conductivity compared to those of the polymers obtained in the presence of Bz(-) and without acidity control. (c) 2006 Elsevier Ltd. All rights reserved.