The influence of the pH of electropolymerization solutions on the properties of polypyrrole films has been studied using potentiodynamic techniques and faradaic impedance spectroscopy. Scanning electron microscopy (SEM), IR and Raman spectroscopies, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were also used for products characterization. Results indicate that, contrary to what happen with the polymer electrogenerated in acid solutions, the films prepared in alkaline media are stable and present good electrochemical activity in basic solutions. Possible explanations for the observed differences are discussed and it is proposed that the pH of electropolymerization medium directly affects chains organization. Electrosynthesis in solutions of increased basicity results in a more compact and closed polymer structure. (c) 2009 Elsevier B.V. All rights reserved.