Multilayer architectures of polyelectrolytes fabricated by the layer-by-layer technique (LbL) on pretreated polymeric and inorganic substrates were studied by contact angle measurements. Poly(diallyldimethylammonium chloride), PDADMAC, and poly(sodium 4-styrenesulfonate), PSS, were used as polyelectrolytes. Contact angle data were used to calculate the van der Waals and Lewis acid-base components of the surface tension of the investigated surfaces. Knowledge of these quantities provides valuable information on surface composition, coating density, and possible interactions of the surface with other substances. Unusual wetting behavior of PDADMAC layers upon prewetting of the multilayer surfaces was found and described in terms of surface tension changes. A model of polymer chain rearrangement upon wetting was proposed to explain this behavior.