The layer-by-layer assembly of polyelectrolytes (poly(allylamine hydrochloride) (PAH) and poly(sodium styrenesulfonate) (PSS)) was carried out using poly(chlorotrifluoroethylene) film that had been chemically modified to contain alcohol functionality (PCTFE-OH) as a substrate for the deposition This neutral surface supports the layer-by-layer assembly when PAH is adsorbed as the first layer. The amount of PAH that adsorbs in the first layer deposition is a function of the pH of the adsorption solution and this was used to control the resulting surface charge density (ammonium ion concentration). Three types of multilayer assemblies were prepared using three experimental protocols. In protocol 1, PAH and PSS were deposited to PCTFE-OH at pH 4. In protocol 2, the first PAH layer was adsorbed at pH 11, and treated with water at pH 4, and subsequent PSS and PAH layers were deposited at pH 4. In protocol 3, the first PAH layer was adsorbed as in protocol 2, and subsequent PSS and PAH layers were deposited at pH 4 with 0.2 M MnCl2 added to the PSS adsorption solutions. The assembly process was monitored using X-ray photoelectron spectroscopy (XPS) and contact angle analysis of isolated multilayer films. The thickness of the individual layers in the assemblies (determined using XPS) depends on both the charge density of the first layer and the ionic strength of the PSS adsorption solution. The stoichiometry of the assembly process (ammonium:sulfonate ratio) also depends on the ionic strength of the PSS adsorption solution. The average individual layer thicknesses for protocols 1,2, and 3, respectively, are 0.3, 0.8, and 4.1 Angstrom thick, as assessed by XPS. Although the layers are extremely thin, XPS and contact angle data indicate that the layers are stratified. Peel tests using pressure-sensitive adhesive tape indicate cohesive failure within a few angstroms of the interface in both the adhesive and the multilayer assemblies.