We report on the fabrication and characterization of electroluminescent devices based on a thin film preparation strategy that involves the alternate polyelectrolyte deposition from aqueous solution for the hole injection/transporting layer combined with a conventional spin-cast method for the luminescent layer (MEH-PPV). Surface plasmon optical techniques are used to monitor the deposition process in-situ, as well as to quantify structural parameters of the final multilayer assemblies. These data are complemented by UV-vis spectroscopy, and X-ray reflectivity measurements. The final devices are functionally characterized in terms of their current-voltage, as well as their luminance-voltage performance.