“…A carbon nanotube (CNT) is one of the revolutionary discoveries in the 20th century. , The exceptional carbon molecular network structure and physical properties like high conductivity, high surface area, and mechanical strength of CNTs have been attracting scientists of different disciplines and researchers to utilize this material for extending its application fields. , Functionalization of CNT is a cutting-edge research topic in the material application field. In general, following methodologies are adopted for functionalization of CNTs: (i) covalent modification, , (ii) self-assembling, (iii) π–π bonding, (iv) encapsulation, , (v) chemical and electrochemical polymerization of organic monomers, , and (vi) nanocomposites. , In all of these modifications, a few monolayer thick target molecules have been adsorbed on the CNT surface. Herein, we first report a specific functionalization of multiwalled carbon nanotube (MWCNT) as benzene moiety π-stacks, designated as MWCNT@[BZ]-π-stack, prepared by the surface-confined electrochemical reaction of the benzene–water cluster ({BZ-H 2 O}) at 1.2 V vs Ag/AgCl in mild acidic conditions (pH 2 KCl–HCl), wherein the diameter of the CNT is increased over 10-fold.…”