Multi-walled carbon nanotubes were functionalized with thiol groups by chemical route. Exploiting the chemical affinity between thiol and gold an assembly of carbon nanotubes was obtained by spontaneous chemical adsorption to gold using Au–S bonds. The multi-walled carbon nanotubes were first chemically cut by acid treatment and then functionalized with short chain thiol (2-aminoethanethiol). Substrate dipping in a suspension of functionalized carbon nanotubes allows them to bond to the gold surface. The resultant products, as well as the intermediate were characterized by means of X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, visible spectroscopy, scanning electron microscopy and atomic force microscopy.