Formation of films from natural polyelectrolytes opens a wide range of application in the areas like tissue engineering, implantation of medical devices or other medical fields. The permeability of films, fabricated from the natural polyelectrolytes by using the layer by layer method, was determined by the cyclic voltamperometry. Using the electroactive molecules that differ in molecular size the porosity of films was examined. We compared the thickness and permeability of multilayer films composed from biocompatible and natural polyelectrolytes with ones composed from the model polycation/polyanion pair, PAH/PSS (polyallylamine hydrochloride/poly(4-styrenesulfonate)). We attributed the difference in the permeability of films with similar thickness to the higher chain stiffness of natural polyelectrolytes. The effect of the anchoring PEI (poly(ethyleneimine)) layer was also examined. (C) 2012 Elsevier Ltd. All rights reserved.