Multiple-walled carbon nanotubes (MWNTs) were chemically modified by a ligand-exchange reaction of ferrocene (Cp-Fe-Cp). The modified MWNTs (Cp-Fe-MWNTs) were next monolithiated by tert-butyllithium and terminated by p-chloromethylstyrene (pMS). The pMS-terminated species (pMS-CpFe-MWNTs) were then functionalized with living polystyryllithium anions via anionic polymerization. The resulting polystyrene-functionalized MWNTs exhibited as polymeric nanocomposites and were soluble in common organic solvents showing distinct colors from a neat polystyrene solution. Syntheses results and the characterization data of the functionalized MWNTs, collected from GC-MS, NMR, electron microscopy, and optical spectroscopy, are presented and discussed.