In this study non-covalent interaction of the surface of single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT) with polysiloxanes containing 20 and 80 mol.% of pendant ferrocenyl groups was investigated. Raman spectra revealed charge transfer between ferrocenyl-containing polysiloxanes and SWCNT and preserving of electronic and vibrational structure of SWCNT and MWCNT. The XPS spectra demonstrated the presence of ferrocenyl-containing polysiloxanes on the SWCNT and MWCNT surface. Modification of SWCNT and MWCNT by ferrocenyl-containing polysiloxanes significantly increased dispersibility of carbon nanotubes in chloroform and toluene, which was confirmed by UV spectroscopy. TEM images demonstrated the presence of a polymer layer with a different thickness on the outer wall of SWCNT and MWCNT. In cyclic voltammograms, electrochemical response of ferrocenyl-containing polysiloxanes depended on the type of CNT and the solvent (chloroform, toluene). The modified SWCNT and MWCNT were used for silicone composites preparation. The specific resistance measurements revealed that the lower values were obtained for composites based on SWCNT modified by ferrocenyl-containing polysiloxanes with 20 mol.% of pendant ferrocenyl groups. Our findings benefit surface science and pave a way toward high-performance electrochemical sensors as well as intelligent conductive silicone materials.