Homogeneous, 50-μm-thick, epoxy coatings and composite epoxy coatings containing 2wt% of 130-nm silica particles were successfully synthetized on austenitic stainless steel of the type AISI 316L. The surface morphology and mechanical properties of these coatings were compared and characterized using a profilometer, defining the average surface roughness and the Vickers hardness, respectively. The effects of incorporating the silica particles on the surface characteristics and the corrosion resistance of the epoxy-coated steel were additionally investigated with contact-angle measurements as well as by potentiodynamic polarization and electrochemical impedance spectroscopy in a 3.5wt% NaCl solution. The silica particles were found to significantly improve the microstructure of the coating matrix, which was reflected in an increased hardness, increased surface roughness and induced hydrophobicity. Finally, the silica/epoxy coating was proven to serve as a successful barrier in a chloride-ion-rich environment with an enhanced anticorrosive performance, which was confirmed by the reduced corrosion rate and the increased coating resistance due to zigzagging of the diffusion path available to the ionic species.