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Duplex coating consisting of an inner cerium-based layer and polypyrrole (PPy) film topcoat was electrodeposited onto AISI 304 stainless steel. The cerium-based coating was electrodeposited in solutions containing cerium nitrate at 50 ºC. The polymeric outer layer was electropolymerized in the presence of sodium bis(2-ethylhexyl) sulfosuccinate (AOT). The electrosynthesis was done under potentiostat conditions. The coatings were characterized by scanning electron microscopy (SEM) and energy dispersive x-ray spectrometry (EDX). The morphology of the double-layered cerium polypyrrole film shows a granular structure with the presence of agglomerates of small grains. The anticorrosive performance of the coatings was evaluated in sodium chloride solution by linear polarization, open circuit measurements, and electrochemical impedance spectroscopy (EIS). Single films, cerium layer and PPy coating, and the duplex film all reduce the corrosion rate of AISI 304 stainless steel in NaCl solution. The duplex coating presents an improved corrosion resistance concerning the single films. The combination of the characteristics of the single layers is responsible for the superior corrosion protection efficiency of the double-layered cerium polypyrrole coating.