This investigation reports the atom transfer radical copolymerization (ATRcP) of glycidyl methacrylate (GMA) and 2-ethylhexyl acrylate (EHA). Poly(glycidyl methacrylate) (PGMA) has easily transformable pendant oxirane group and poly(2-ethylhexyl acrylate) (PEHA) has very low T-g They are the important components of coating and adhesive materials. Copolymerization of GMA and EHA was carried out in bulk and in toluene at 70 degrees C at different molar feed ratios using CuCl as catalyst in combination with 2,2'-bypyridine (bpy) as well as N,N,N'N '',N ''-pentamethyl diethylenetriamine (PMDETA) as ligand. The molecular weight (M-n) and the polydispersity index (PDI) of the polymers were determined by GPC analysis. The molar composition of the copolymers was determined by H-1 NMR analysis. The reactivity ratios of GMA (r(1)) and EHA (r(2)) were determined using Finemann-Ross and Kelen-Tudos linearization methods and those had been compared with the literature values for conventional free radical copolymerization. The thermal properties of the copolymers were studied by DSC and TGA analysis. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6526-6533, 2009