Polyaniline (PAni) coatings are synthesized polymerizing aniline chemically, by oxidation in presence of (NH4)(2)S2O8, and electrochemically, by using a pulse potentiostatic procedure. Both types of PAni coatings are compared with respect to their potentiodynamic behavior, electrochemical stability and surface morphology. Additional comparison is made by investigating the electrocrystallisation of copper. The chemically and electrochemically PAni coatings exhibit different surface morphologies but nevertheless show identical redox behavior and stability with respect to multiple cycling. The different PAni morphologies have a marked influence on the metal crystallization process, the chemical coatings allowing for an easier copper nucleation and growth. (C) 2003 Elsevier B.V. All rights reserved.