A ferrocene‐containing oligoorganosiloxane with a number‐average degree of polymerization of 8.8 and a number‐average molecular weight of 3200 is synthesized by hydrolytic condensation of 3‐aminopropyltriethoxysilane followed by chemical modification of the resulting oligomer with acetylferrocene. Its structure is characterized by MALDI‐TOF, NMR and IR spectroscopy. 1H NMR spectroscopy shows the predominance of more thermodynamically stable units containing anti‐configuration Schiff bases. Using IR spectroscopy as well as experimental determination of surface energy and its polar (acid–base) and dispersion components, the covalent immobilization of ferrocene‐containing oligoorganosiloxane on a glass surface after heating at 110°C is shown. The formed coating provides hydrophobization, acid–base indifference of the glass surface and serves as a precursor for the formation of magnetically soft materials after pyrolysis in argon already at 350°C. The main stages of ferrocene‐containing oligoorganosiloxane thermal destruction in an inert atmosphere and the formation of a mixture of iron and silicon oxides during its thermal oxidative destruction are established by combination of TGA/DTA, IR spectroscopy and elemental analysis. The proposed approach opens up new possibilities for functionalizing silicates surfaces, creating magnetic glasses, as well as regulating surface energy and its components.