Glow Discharge Optical Emission Spectroscopy (GDOES) has been developed to perform depth profiles of thick metallic films, in tens of microns range. GDOES spectroscopy can also be used to analyze thin organic polymer films since this technique has a great potential thanks to its high depth resolution, multi-element capability, sensitivity, and adaptability to solids or films and to conducting or non-conducting samples. In particular thin electrodeposited conducting polymer films remain an unexplored field of investigation for GDOES technique. However GDOES was used in this work to analyze electrodeposited polyaniline films, in addition to other techniques such as profilometry, electron microscopy and X-ray diffraction (XRD). More precisely polyaniline thin films were electrodeposited from HCl solutions and the presence of an anilinium chloride excess at the top surface of the polymer film was demonstrated using GDOES and XRD. Rinsing of these films with water led to the removal of this excess and to the partial dedoping of the polymer film due to the porous structure of polymer films. Polyaniline thin filmswere also electrodeposited from H2SO4 solutions and an anilinium hydrogen sulfate was similarly observed at the top surface of the polymer. This excess was removed by rinsing, contrary to hydrogen sulfate anions incorporated into the polymer film during the electrochemical polymerization that were not completely expulsed from the polyaniline films as proved using GDOES. (C) 2013 Elsevier B. V. All rights reserved.