Free-radical homopolymerization of N-isopropyl acrylamide (NIPA, monomer 1) and copolymerizations of NIPA with glycidyl methacrylate (GMA, monomer 2) were conducted in deuterated dioxane at 70 °C. The conversion of the monomers was followed by 1H NMR spectroscopy. After the polymerization reactions, the polymers were precipitated and analyzed. Reactivity ratios were determined using both Fineman–Ross and extended Kelen–Tüdõs methods. Values obtained with these two methods were r1 = 0.39, r2 = 2.69 and r1 = 0.30, r2 = 2.66, respectively. In both cases, r ∼ 1, which is indicative of an ideal copolymerization resulting in a first-order Markov distribution of the monomers in the final copolymer. The compositional heterogeneities of the polymers were estimated by following the instantaneous copolymer compositions as functions of conversion. Given the different reactivities of the two monomers, it is concluded that a copolymer with a homogeneous distribution of monomers may be obtained not by a batch reaction but by slowly and continuously adding GMA to the polymerizing reaction mixture.