We report a new strategy to obtain high performance polymer-grafted multi-walled carbon nanotubes (MWCNTs). Chlorophenyl-functionalized MWCNTs, obtained through the in situ generation and reaction of diazonium compounds, were subjected to polymerization in the presence of Na 2 S and 1,4dichlorobenzene in order to yield MWCNTs covalently functionalized with poly(p-phenylene sulfide) (PPS) oligomers. The MWCNT functionalization and the PPS oligomeric chain growth can be controlled throughout accessible experimental variables, including the possibility to carry out the whole process in a one-pot reaction. This represents an efficient and facile route to develop covalently grafted MWCNTs beyond those reported so far for the same polymer. These materials are promising fillers for the production of high performance PPS-based composite materials, due to the improvement of the filler-matrix compatibility. The manufacturing and characterization of some test samples show that oligomer-grafted MWCNTs induce the suppression of the intrinsic confinement effect imposed by the nanofiller, as for the observation of an increase in the PPS crystallinity. An outstanding increase in the PPS thermal stability and mechanical properties is also observed, as compared to bare MWCNTs, while leaving the electrical properties unharmed.