Novel multilayer thin films that consist solely of cross-linked single component layers are generated by a selective cross-linking of the poly(vinyl amine) (PVAm) layers in [PVAm/poly(acrylic acid) (PAA)](n) thin films constructed either on silica particles or silicon wafers, followed by the removal of PAA. The surface topography of the (PVAm), multilayer thin films, before and after the adsorption of human serum albumin (HSA), has been studied by atomic force microscopy on the freeze-dried films. The decrease of the Ark average roughness of the film after the adsorption of HSA F showed the protein was adsorbed into the (PVAm)(n) film making these films potential reservoirs for proteins.