Conducive polyelectrolyte multilayer films composed of conducive anionic poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) and insulating cationic polydiallyldimethylammonium chloride (PDDA) were successfully prepared by layer-by-layer method. The (PDDA/PEDOT:PSS)(n) multilayer thickness is affected by the PDDA concentration ranging from 0.25 g.L-1 to 1 g.L-1 as well as the number of deposited bilayers and the type of salts used as electrolyte (BaCl2 or NaCl). More precisely, film thickness measured by profilometry increases with PDDA concentration, number of adsorbed bilayers and with the presence of Ba2+ cations. From UV-Visible absorbance spectroscopy, we showed that the amount of adsorbed PEDOT:PSS is greater when PDDA concentration increases and that PEDOT is still incorporated into the multilayer film especially when divalent ions are employed to improve the film growth. Water contact angles were measured on (PDDA/PEDOT:PSS)(n) films with PEDOT:PSS as the outerlayer. Films are more hydrophobic in the presence of Ba2+ which is probably due to a modification of the PEDOT:PSS core/shell structure. A percolation threshold leading to electrical conduction was determined as a function of the number of adsorbed bilayers. The effect of several parameters such as PDDA concentration, type of salt and temperature on conductivity and activation energy was investigated.