One of the remarkable choices for active smart window technology is adopting a metal active layer via reversible metal electrodeposition (RME). As the metal layer efficiently blocks the solar energy gain, even a hundred-nanometer-thick scale, RME-based smart window has great attention. Recent developments are mainly focused on the various cases of electrolyte components and composition meeting technological standards. As metal nanostructures formed through the RME process involve plasmonic phenomena, advanced analysis, including plasmonic optics, which is beyond Beer–Lambert’s law, should be considered. However, as there is a lack of debates on the plasmonic optics applied to RME smart window technology, as research is mainly conducted through an exhaustive process. In this paper, in order to provide insight into the RME-based smart window development and alleviate the unclear part of plasmonic optics applied to the field, finite-difference time-domain electromagnetic simulations are conducted. In total, two extremely low-quality (Cr) and high-quality (Mg) plasmonic materials based on a nanoparticle array are considered as a metal medium. In addition, optical effects caused by the metal active layer, electrolyte, and nanoparticle embedment are investigated in detail. Overall simulations suggest that the effective refractive index is a decisive factor in the performance of RME-based smart windows.