Gold nanoparticle/alkanedithiol films were prepared via layer-by-layer self-assembly. For the assembly process, dodecylamine-stabilized Au nanoparticles with an average size of 4 nm and alkanedithiols with different alkylene chain lengths (C-6, C-9, C-12, C-16) were used. The thickness of the films was determined by AFM and ranged between 26 and 34 run. FE-SEM and TEM images indicate that the particle size within the film materials was similar to that of the dodecylamine-stabilized particles used for film preparation. The composition of the films was analyzed by XPS. The absence of the nitrogen signal indicated that the dodecylamine ligands were quantitatively exchanged by alkanedithiol molecules during film assembly. Two sulfur signals were observed, which could be assigned to sulfur bound to gold (S-Au) and to free thiol groups (S-H). As indicated by the relative signal intensities, about 60% of the alkanedithiol molecules were bound with both ends to the nanoparticles, whereas 40% were bound with only one thiol group. The C/S ratio was in good agreement with the stoichiometry of the alkanedithiol molecules. All films showed linear current-voltage characteristics. Conductivity measurements at variable temperature were consistent with an Arrhenius-type activation of charge transport. Using an activated tunneling model for describing the charge transport properties, we obtained an electron tunneling decay constant of beta(N) = 0.61 or 0.71, depending on the method used for data analysis. When the films were dosed with vapors of toluene and tetrachloroethylene, the resistance of the films increased reversibly. This response increased exponentially with increasing length of the alkanedithiol molecules. The chemical selectivity of the films corresponded essentially to the solubility properties of the alkanedithiol molecules.