Confocal Raman spectroscopy and DRS-FT-IR spectroscopy were used to study three types of coatings o pure titanium prepared by the electrophoretic deposition (EPD). The tests based on the comparison of the spectroscopic data for the multi-walled carbon nanotubes/polysiloxane (MWCNTs/PS) coating with the results obtained for those of pure MWCNTs and PS. The studies have shown that micro-Raman confocal spectroscopy applied to the coatings containing MWCNTs is a valuable tool that allows to determine the characteristics of MWCNTs which could be related to the functional properties of the coatings applied on metallic surfaces. Infrared spectroscopy studies of the MWCNTs/PS nanocomposite coating provided data on the interactions between its two components. The comparison of this information with the results obtained for the pure PS coating allowed to characterize the changes in the polymer structure caused by the presence of carbon nanotubes (CNTs). The coatings were also examined using scanning electron microscopy (SEM) and energy dispersive X-ray microanalysis (EDS).