Statistical copolymers of N-vinylpyrrolidone (NVP) with 2(dimethylamino) ethyl methacrylate (DMAEMA) were prepared by Reversible Addition-Fragmentation chain Transfer Polymerization (RAFT), employing three different RAFT agents: [(O-ethylxanthyl)methyl]benzene, [1-(O-ethylxanthyl)ethyl]benzene, and O-ethyl S-(phthalimidylmethyl) xanthate. The reactivity ratios were estimated using the Fineman-Ross, inverted Fineman-Ross, Kelen-Tudos, and extended Kelen-Tudos graphical methods, along with the computer program COPOINT. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length. All the methods indicate that the DMAEMA reactivity ratio is much greater than the one of NVP, thus, the statistical copolymers are in fact pseudo-diblocks. The glass-transition temperature (T-g) values of the copolymers were measured by Differential Scanning Calorimetry. Furthermore, a systematic and detailed investigation has been done, on the thermal degradation of the copolymers compared with the respective homopolymers, by Thermogravimetric Analysis, within the framework of the Ozawa-Flynn-Wall and Kissinger methodologies. Apparently, the thermal stability of the copolymers is influenced by both monomers and by the structure of the thiocarbonylthio end groups due to the RAFT agents. (C) 2017 Wiley Periodicals, Inc.