The influence of a first (anchoring) layer and film treatment on the structure and properties of polyelectrolyte multilayer (PEM) films obtained from polyallylamine hydrochloride (PAH) and polysodiurn 4-styrenesulfonate (PSS) was studied. Branched polyethyleneimine (PEI) was used as an anchoring layer. The film thickness was measured by ellipsometry. Complementary X-ray reflectometry and AFM experiments were performed to study the change in the interfacial roughness. We found that the thickness of the PEM films increased linearly with the number of layers and depended on the presence of an anchoring PEI layer. Thicker films were obtained for multilayers having PEI as the first layer comparing to films having the same number of layers but consisting of PAH/PSS only. We investigated the wettability of PEM surfaces using direct image analysis of the shape of sessile water drops. Periodic oscillations in contact angle were observed. PAH-terminated films were more hydrophobic than films with PSS as the outermost layer. The effect of long time conditioning of PENI films in solutions of various pH's or salt (NaCl) concentrations was also examined. Salt or base solutions induced modification in wetting properties of the polyelectrolyte multilayers but had a negligible effect on the film thickness. (c) 2006 Elsevier Inc. All rights reserved.