AbstractPolyaniline (PANI) films may be developed on metallic substrates by a variety of electrochemical techniques. In the present work, PANI films were electrodeposited on AISI 316L stainless steel substrates by cyclic voltammetry (CV), chronoamperometry (CA), and chronopotentiometry (CP) with the objective of comparing the efficacy of each method, based on the integrity of the developed films. Cyclic voltammetry and anodic polarization were used to determine optimal electrodeposition parameters for the development PANI films using the CA and CP methods. The structure and morphology of the coatings were characterized by scanning electron microscopy, energy‐dispersive x‐ray spectroscopy, Fourier‐transform infrared spectroscopy, and ultraviolet–visible spectroscopy. Among the evaluated techniques, CV led to the formation PANI films with the best homogeneity as well as the lowest number of defects, such as cracks or pores. Subsequently, the corrosion resistance of AISI 316L steels with and without PANI was compared in a physiological saline solution (0.9% NaCl). Potentiodynamic polarization tests indicated that the PANI‐coated samples exhibited lower corrosion current density values (0.012 vs. 0.018 μA/cm2) and lower passive current density values (0.04 vs. 0.06 μA/cm2) in comparison to the bare AISI 316L steel. Additionally, long‐term monitoring by electrochemical impedance spectroscopy revealed that PANI films consistently exhibited superior polarization resistance up to 32 days of exposure in the 0.9%NaCl solution (233,000 vs. 207,000 Ωcm2).