In this article, a series of hybrid coatings were prepared and characterized. At first, polydimethylsiloxane modified with siliane coupling agent was copolymerized with acrylate monomers by free radical polymerization to get the hybrid resins. Due to the combination of covalent bond, the prepared hybrid resins were uniform and transparent. Then a series of hybrid resins were cured with tetraethoxysilane and dibutyltin dilaurate as the crosslinker and catalyst, respectively. The blends were loaded onto the substrate, such as tin plate, steel panels, or flat glass, and cured by heating to form hybrid coatings. To study the factors on the properties of the prepared hybrid resins and cured coatings, various measurements were carried out, such as FTIR, TGA, DSC, laser optical microscope, water contact angles, pencil scratch hardness, and the electrochemistry test. Thanks to the combination of covalent bond, the two components dispersed uniformly in the prepared hybrid resins and no cracks were observed from the cured hybrid coatings with an optical microscope. With excellent mechanical properties, thermal stability, corrosion resistance, and hydrophobic property, the prepared hybrid coatings can find application in the heavy-duty chemical industry.