Poly(3,4-ethylenedioxypyrrole), PEDOP, is a versatile compound, which has attracted significant scientific interest in the recent years. The wide range of its actual and prospective applications underlines the need for a comprehensive study of this material and identification of factors, allowing the physicochemical properties of PEDOP and its derivatives to be tailored for specific purposes. In this paper, we present the results of our investigation of the physicochemical properties of PEDOP, involving electrochemical, spectroelectrochemical and microscopic analysis. The electrochemical synthesis of PEDOP was performed in solvents of varying polarity and protic/aprotic nature, i.e. H2O, CH3CN and CH2Cl2, by means of cyclic voltammetry. Raman spectroscopy was applied in order to investigate the chemical structure of PEDOP synthesised under varying conditions. ESR measurements allowed the observation of changes in spin concentration as a function of applied potential and analysis of the stability of formed radical anions. UV–vis spectroelectrochemistry was applied to determine the value of optical band gap of PEDOP. The surface morphology of fabricated PEDOP layers was investigated via scanning electron microscopy.