This paper describes the methodology of the preparation and analyses of the structure and anticorrosion properties of silane coatings modified with poly(3,4-ethylenedioxythiophene) (PEDOT) with phosphododecamolybdic acid (PMo12). Protective coatings, consisting of vinyltrimethoxysilane (VTMS), PEDOT powder with PMo12 admixture (at different concentrations), and ethanol, were deposited on X20Cr13 and 41Cr4 steels by immersion. The physicochemical properties of these silane coatings (e.g., surface morphology, thickness, roughness, and adhesion to the substrate) were elucidated using a digital microscope, a Fourier transform infrared spectrophotometer with attenuated total reflectance, and various electrochemical diagnostic techniques. Protective properties were assessed in acidified sulfate solutions with and without chloride ions (pH 2). Experimental results have shown that this coating displayed the effective protection of steel against general and pitting corrosion, stabilized the corrosion potential in the passive state, and provided barrier protection.