Self-assembled films of Poly(o-ethoxyaniline) (POEA) doped with HCl alternated with sulfonated lignin (SL) were successfully produced under different pHs and their kinetics of formation studied. The adsorption at lower pi-Is is faster due to the greater electrostatic attraction between the POEA and the SL covered substrate, but a lower amount of POEA is deposited due to ch;uge repulsion of additional POEA chains and conformational steric hindrance. At higher pHs the adsorption of POEA cakes longer but it is greater due to the contribution of hydrogen bonding interactions, lower charge repulsion between POEA chains and a more compact polymer conformation. Adsorption of POEA/SL multilayers could be carried out in different types of substrates. Atomic force microscopy (AFM) employed to investigate the morphology of the alternated layers showed that POEA layers exhibited a granular rough aspect, while SI, layers presented a much smoother surface. (C) 2001 Elsevier Science Ltd. All rights reserved.