Multi-walled carbon nanotubes (MWCNTs) have been functionalized through perfluoropolyether (PFPE) radicals obtained by thermal decomposition of linear PFPE peroxide. The reactivity of MWCNTs with PFPE peroxide has been compared with the direct fluorination of MWCNTs using elemental fluorine in mild conditions. The experimental results indicated that the functionalization with PFPE peroxide and the direct fluorination with elemental fluorine were suitable techniques to modify and control the physical-chemical properties of MWCNTs. After the introduction of PFPE chains on the MWCNT surface, the wettability of MWCNTs changed from hydrophilic to superhydrophobic, because the low surface energy properties of PFPE were transferred to the MWCNT s...