Although metallic alloys commonly used as prosthetics are durable and mechanically strong, they are often bioinert and lack antibacterial properties. Implementing a bioactive glass material with antibacterial properties as a coating on a metallic substrate provides mechanical strength and bioactivity, as well as antibacterial properties. Many coating methods have been extensively investigated; however, most of them can be expensive, are difficult to scale up, or do not form thin films, which could prevent their translation to clinical practice. The formation of thin films by spin-coating multi-component solution–gelation (sol–gel)-derived glass with antibacterial and bioactive properties has not been achieved previously. For this study, stainless steel 316L substrates were spin-coated with a sol–gel-derived bioactive and antibacterial glass coating in SiO2 58.3–​P2O5 7.1–​CaO 25.6–​Al2O5 5.4–​Ag2O 2.1–​Na2O 1.5 wt% system (Ag-BG). A sol–gel processing condition that avoids elemental separation upon spin-coating when sintering happens at below the calcination temperature (500 °C) has been developed. This work demonstrates that silver reduction occurs when the concentrations of other cations such as Ca2+ and Na+ in the solution increase. Increasing the stirring duration time prior to the increase of cations, Ag+ ions are stabilized by aluminum tetrahedra, and their reduction to metallic silver does not occur. This study also shows that large dilution ratios (water:​tetraethyl ortho­silicate) greater than 25:1, accompanied by long stirring durations, produce morphologically homogeneous coatings. Using this strategy, thin films were formed with antibacterial properties against methicillin-resistant Staphylo­coccus aureus (MRSA) biofilm and biological responses that promote eukaryotic cell adhesion and proliferation. In total, the improved synthesis strategy opens new avenues for the development of novel bioactive and antibacterial thin-film coatings, as it reveals the processing characteristics that control the physico­chemical and morphological properties of the formed films.