Two chemical structural isomers, 2-hydroxyethyl methacrylate and ethyl ␣-hydroxymethyl acrylate, were copolymerized with dimethyl amino ethyl methacrylate in bulk at 50°C with 1.0 ϫ 10 Ϫ2 mol/L 2,2Ј-azobisisobutyronitrile as an initiator. Experiments showed differences in the values of the monomer reactivity ratios due to electronic or steric contributions to the cross-propagation reaction. The homopolymer glass-transition temperature (T g ), along with the intramolecular and intermolecular structure and Johnston's equation, enabled a description of the experimental variations of the copolymer T g .