Here, we report on a novel method of incorporating carbon nanotubes into a polymer matrix by using carbon nanotubes as a chain transfer agent (CTA) in Reversible Addition-Fragmentation chain Transfer (RAFT) polymerisations. The dithioester RAFT agents were covalently linked to multi-walled carbon nanotubes (MWCNTs) via a method, which involved the reaction of acyl halide MWCNTs with a magnesium chloride dithiopropanoate salt. Polystyrene (PSt) was subsequently grafted from the MWCNT surface via the core-first technique, which implies an outward growth of polymer chains from the core, using the R-group approach. The structure and morphology of the hybrid nanomaterials were investigated using FTIR, NMR, thrmogravimetric analysis (TGA) and atomic force microscopy (AFM) techniques. The results showed that the MWCNT chain transfer agent could be successfully used to mediate the growth of polystyrene polymer from the MWCNT surface via the living radical polymerisation approach.