Poly(glycidyl methacrylate), PGMA, was prepared via ATRP in bulk solution, and its epoxy groups were further acid-hydrolyzed in order to obtain a polymer with glycerol moieties (noted POH). The POH chain end C-Br bonds were subjected to a nucleophilic attack by NaN3, resulting in azide-terminated POH (POH-N-3). The CNTs were modified by in-situ-generated alkynylated diazonium cations from the para-alkynylated aniline of the formulas H2N-C6H4-C C-H, yielding CNT-C6H4-C- C-H nanotubes. The azide-functionalized polymer POH-N-3 was clicked to the alkynyl-modified CNTs giving CNT@POH hybrids, which were further subjected to an oxidation resulting in carboxylated polymer-modified CNTs (noted CNT@PCOOH). The as-designed hairy CNTs served as efficient platforms for the in-situ synthesis and massive loading of 3 nm sized palladium nanoparticles (NPs). The CNT@ PCOOH@Pd heterostructures prepared so far exhibited an efficient catalytic effect in the C-C Suzuki coupling reaction and were regenerated up to four times without any significant loss of catalytic activity.