In this study, we present a novel multifunctional coating that enhances the adhesion, surface stability, water repellency, and corrosion resistance of electrodeposited polythiophene (PTH) coatings. By incorporating a thienyl-substituted silane coupling agent as a surface modifier, we significantly improve adhesion to steel substrates. The addition of a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) topcoat further increases water repellency. Spectroscopic analyses confirm successful silanization, indicating robust chemical bonding between the substrate and the coating, while adhesion tests reveal minimal delamination. Notably, the coating exhibits superhydrophobic and superoleophilic properties, enabling efficient oil-water separation, which is advantageous for environmental applications such as oil spill remediation and wastewater treatment. This approach aligns with green and sustainable chemistry principles by extending the lifespan of PTH coatings, reducing the need for frequent reapplications, and minimizing environmental impact. Overall, our method sets a new benchmark for developing durable, hydrophobic, and multifunctional protective coatings, offering promising avenues for future research and industrial applications.