Abstract: Several hydrophobic acrylamide derivatives: the N-tert-butylacrylamide (TBAm), the N-octadecylacrylamide (ODAm) and the N-diphenylmethylacrylamide (DPMAm) have been polymerized by reversible addition–fragmentation chain transfer (RAFT) process in the presence of azobis(isobutyronitrile) (AIBN) and tert-butyl dithiobenzoate (tBDB) as initiator and reversible chain transfer agent (CTA), respectively. Homopolymerizations were compared as regards to kinetics and molecular weight (MW) control, and the results were discussed according to the monomer structure and to the influence of several experimental parameters, such as the [CTA]/[AIBN] ratio and the [Monomer]/[CTA] ratio. TBAm and ODAm monomers exhibited a well controlled polymerization (polydispersity index (PDI) below 1.3 for number average molecular weight (Mn) until 30,000gmol-1) over a wide range of conversion (until 70%), whereas DPMAm conversion remained below 20% partly due to steric hindrance. The molecular weights of several poly(TBAm) samples determined by four independent analytical techniques, size exclusion chromatography/on-line light scattering detector (SEC/LSD), 1H NMR, 13C NMR and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS), were in agreement, close to the theoretical ones. Moreover, the MALDI-TOF MS analyses suggested the presence of parasite chains resulting from irreversible termination onto RAFT intermediate radicals. [Copyright &y& Elsevier]