AbstractStatistical glycidyl methacrylate/butyl acrylate copolymerization, at three different feed monomer compositions (75:25, 50:50, and 25:75), was carried out under atom transfer radical polymerization conditions with ethyl 2‐bromoisobutyrate as an initiator, copper chloride as a catalyst, and N,N,N′,N″,N″‐pentamethyldiethylenetriamine as a ligand in 50% (v/v) toluene and diphenyl ether solutions and at 30 °C. Linear first‐order kinetics, linearly increasing molecular weight with conversion, and low polydispersities were observed for all the copolymerizations. The apparent propagation constant obtained for each molar fraction in the feed had similar values in the two solvents and increased as the glycidyl methacrylate molar fraction in the feed increased. The monomer reactivity ratios, 2.78 ± 0.32 for glycidyl methacrylate and 0.16 ± 0.07 for butyl acrylate, were estimated with the extended Kelen–Tüdos equation, and the copolymer compositions were determined by 1H NMR spectroscopy. The cumulative copolymer compositions as a function of conversion for the different molar fractions in the feed were quite consistent with the theoretically calculated values from the Mayo–Lewis terminal model. Moreover, the cure behavior of a copolymer with a commercial linear diamine was also analyzed by differential scanning calorimetry. A single exothermic peak was observed for a nonisothermal curing reaction, indicating the clear potential of the obtained copolymers for epoxy applications. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1807–1816, 2006