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In this study, 6061 Al alloy was galvanostatically anodized under the Plasma Electrolytic Oxidation (PEO) condition. A factorial design of 22 was carried out using two variables (anodization time and presence of silver in the electrolyte) on two levels, i.e., 20 and 60 min of anodization and the absence/presence of silver ions in the electrolyte. The Al anodization was performed in sodium silicate electrolyte, applying a constant current density of 20 mA cm−2. The oxide characterization was performed by Scanning Electron Microscopy (SEM), surface roughness analysis (RMS), Energy Dispersive Spectroscopy (EDS), Rutherford Backscattered Spectroscopy (RBS), and Grazing Incidence X-ray Diffraction (GIXRD). The SEM micrographs revealed an irregular porous structure with cracks on the oxide surface composed of a thin crystalline layer of γ-Al2O3 over the Al substrate. From EDS and RBS analysis, it was possible to identify the elements Al, O, Si, Ag, and Na, demonstrating that a shorter anodization time (20 min) led to a significant amount of silver deposits on the outer layer of the oxide coating, mainly deposited in the surroundings of the pores. Conversely, the silver content on the PEO film anodized for 60 min was meager. These results demonstrated that the anodization time was the critical control variable for the amount of silver deposited over the oxide film. The shorter the anodizing time, the higher the silver content on the PEO coating.