The corrosion resistance of sol-gel-derived, organic-inorganic, silica-based hybrid coatings was studied. Hybrid sols were prepared by copolymerizing tetraethylorthosilicate (TEOS) and 3-methacryloxypropyltrimethoxysilane (MPS) with a two-step acid-catalyst process. Hybrid coatings were dip-coated on 304 and 316 stainless steel substrates and annealed at 300°C for 30 minutes. The adhesion, flexibility, and biocompatibility of the coatings were examined. Hybrid coatings were found to be relatively dense, uniform and defect free. Electrochemical analyses showed that the coatings provided excellent corrosion protection by forming a physical barrier, which effectively separated the anode from the cathode. In addition, further experimental results revealed that the corrosion patterns are strongly dependent on the nature of the stainless steel substrates. Some possible mechanisms for corrosion breakdown associated with each type of substrate are also introduced.