The polycondensation sol–gel reaction of 5-methylresocinol and formaldehyde with additional compounds in reaction media is a relatively simple way to produce modified aerogels. In order to obtain aerogels with a large surface area and high porosity, the conditions for gel formation, the solvent exchange process before drying, and the supercritical drying process were optimized. A successful attempt was made to introduce ferrocene units into 5-methylresocinol-formaldehyde-based aerogels. The resulting aerogels are amorphous substrates, and no aggregated ferrocene units were found in their structures. All of the aerogel samples that were obtained are structurally similar despite differences in the original ferrocene units and their initial concentration. It was found that the inclusion limit of ferrocene structural blocks into an aerogel is ~6% wt. The structures of the inclusions in which all of the Fe atoms in the aerogel substrates were present in ferrocene/ferrocenium at an approximate ratio of 60/40 to 55/45 were confirmed by X-ray photoelectron spectroscopy and Mössbauer spectroscopy. Aerogels with ferrocene/ferrocenium inclusions are likely to exhibit reversible redox activity in reactions with gaseous reagents.