Reversible addition-fragmentation chain transfer polymerization at 70 C in N,N-dimethylformamide was used to prepare poly(N-isopropylacrylamide-co-N,N- dimethylacrylamide) copolymers in various compositions to afford well-defined polymers with pre-determined molecular weight, narrow molecular weight distribution, and precise chain end structure. The copolymer compositions were determined by 1H NMR spectroscopy. The reactivity ratios of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMA) were calculated as r NIPAM = 0.838 and r DMA = 1.105, respectively, by the extended Kelen-Tüdös method at high conversions. The lower critical solution temperature of PNIPAM can be altered by changing the DMA content in the copolymer chain. Differential scanning calorimetry and thermogravimetric analysis at different heating rates were carried out on these copolymers to understand the nature of thermal degradation and to determine its kinetics. Different kinetic models were applied to estimate various parameters like the activation energy, the order, and the frequency factor. These studies are important to understand the solid state polymer degradation of N-alkyl substituted polymers, which show great potential in the preparation of miscible polymer blends due to their ability to interact through hydrogen bonding. © 2012 Akadémiai Kiadó, Budapest, Hungary.