AISI 316 steel has good corrosion behavior and high-temperature stability, but often prolonged exposure to temperatures close to 700 °C in aggressive environments (e.g., in boilers and furnaces, in nuclear installations) can cause problems that lead to accelerated corrosion degradation of steel components. A known solution is to prepare alumina ceramic coatings on the surface of stainless steel. The aim of this study is to obtain aluminum oxide ceramic coatings on 316L austenitic steel, by Plasma Electrolysis Oxidation (PEO), using a pulsed unipolar power supply. The structures obtained by PEO under various experimental conditions were characterized by XPS, SEM, XRD, and EDS analyses. The feasibility was proved of employing PEO in NaAlO2 aqueous solution using a pulsed unipolar power supply for ceramic–like aluminum oxide films preparation, with thicknesses in the range of 20–50 μm, and a high content of Al2O3 on the surface of austenitic stainless steels.