Controlled living radical polymn. (CLRP) of vinyl chloride (VC) via the reversible addn.-fragmentation chain transfer (RAFT) process is reported for the first time. The cyanomethyl methyl(phenyl)carbamodithioate (CMPCD) was found to be an efficient RAFT agent enabling the CLRP polymn. of VC monomer under certain exptl. conditions. Two different radical initiators, having very distinct half-life times at room temp., were employed in this study. The kinetic studies of RAFT polymn. of VC show a linear increase of the mol. wt. with the monomer conversion and the lowest polydispersity (PDI) ever reported for poly(vinyl chloride) (PVC) synthesized with CLRP method (PDI ∼ 1.4). The resulting PVC was fully characterized using the matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), 1H NMR spectroscopy (1H NMR), and gel permeation chromatog. (GPC) techniques. The 1H NMR and MALDI-TOF-MS anal. of PVC prepd. via RAFT polymn. method have shown the absence of structura