In this study, different loading ratios of epoxy resin (E) and epoxidized soybean oil (ESO) were introduced into acrylic-silicone polymeric blend with the presence of polyisocyanate (NCO) as the curing agent. The developed coating systems were applied on pretreated cold rolled mild steel substrates and the overall performances were investigated by means of Fourier transform infrared (FTIR) spectroscopy, contact angle measurements (CA), UV-vis analysis, thermogravimetric analysis (TGA), electrochemical impedance spectroscopy (EIS) and salt spray test. Moreover, the physico-mechanical properties of all developed coating systems were investigated. The obtained results revealed the ability of the combination of E and ESO at a certain concentration specifically, 9:1, to enhance the overall performance of the polymeric matrix as optimum curing level, better wettability, good physical-mechanical characteristics, thermal stability and significantly enhanced corrosion resistance were observed. The results also demonstrated the ability of the fabricated single-layer coating system to serve as a primer, topcoat or single coating system that has promising potential to be applied for decorative, self-cleaning, thermal insulation and corrosion protection purposes.