Poly(lauryl acrylate) P[LA] of various molar masses were prepared via reversible addition–fragmentation chain transfer (RAFT) polymerisation and Cu(0)-mediated radical polymerisation, for the purpose of improving the dispersion and interfacial adhesion of MWCNTs with polymers such as isotactic poly(propylene) (iPP). Lauryl acrylate (LA) was polymerised via RAFT to high conversion (95%), furnished polymers in good agreement with theoretical Mn with dispersity increasing with increasing Mn. LA polymerised via the Cu(0)-mediated method to full conversion (>98%), gave polymers in good agreement with theoretical Mn and low dispersity (Đ ≈ 1.2) for lower molar mass polymers. Low molar mass tailing was also observed for P[LA] via Cu(0)-mediated polymerisation for higher molar mass polymers. Thermogravimetric analysis (TGA) of P[LA] via RAFT showed an onset of degradation occurred at ≈340–350 °C, however, this decreased to ≈250–260 °C for lower molar mass polymers. TGA of the RAFT agent revealed an onset of degradation of ≈200–250 °C. Free radicals generated from thermal degradation of end groups did not influence the thermal stability of the P[LA] backbone and ‘unzipping’ commonly seen with methacrylates was not observed. TGA analysis of P[LA] via the Cu(0)-mediated method revealed a similar degradation profile to that of P[LA] via RAFT. The thermal stability of P[LA] is sufficient to allow for melt processing with iPP. P[LA] via RAFT mixed with MWCNTs showed an adsorption of ≈10–25 wt% P[LA] on to the MWCNTs. The onset of thermal degradation of the P[LA] remained unchanged after adsorption on to the MWCNTs. P[LA] via the Cu(0)-mediated method adsorbed up to 85 wt% and an increase in thermal stability of ≈50 °C was recorded. Increasing P[LA] and MWCNT concentration independently also resulted in an increase in the level of adsorption, possibility due to increased CH–π interaction. The difference in thermal stability could possibly be due to heat transfer from the P[LA] to the MWCNTs, resulting in delayed pyrolysis of P[LA]. Size exclusion chromatography (SEC) and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) of P[LA] after heating to 200 °C for 30 min in air showed loss of end groups but, the P[LA] backbone remained preserved for both polymer types. Evidence from transmission electron micrographs (TEM) shows the P[LA] adsorbing onto the MWCNT surface. Melt processing composites of P[LA] via Cu(0)-mediated with MWCNTs and iPP was possible as the P[LA] was thermally stable during the both extrusion and in the TGA when studied post melt mixing.