The molecular geometry and electronic structure of styrene and methyl methacrylate as well as corresponding radicals formed by the addition of a methyl radical to the beta -carbon of the monomer were determined using the density functional theory at the B3LYP/6-311+G** level. Results were in good agreement with the theoretical and experimental data available in the literature. Full optimized molecular geometry of methyl methacrylate showed the trans form of the molecule. Monomers transformed into corresponding radicals preserved the main structural parameters of substituents whereas bonds between substituents and adjacent radical carbon atoms shortened. It was found that the correlation of the theoretically calculated electronic parameters for monomers and the corresponding radicals with the Q and e parameters from the Alfrey-Price scheme strongly depends on the level of calculations. Application of the higher level of theory including the correlation effect changes the relationship discussed in the literature between energy (E-y) of formation of a radical from the monomer, the experimental e parameter, and the Q parameter and monomer/average electronegativity, respectively. The total atomic spin density at the radical carbon atom correlated with the radical parameter P in the Alfrey-Price scheme was computed to be higher for the methoxycarbonyl-l-methyl-ethyl radical when compared with the I-phenyl-propyl radical. These values are in good agreement with the localization energies and the P values determined from the kinetic measurements for macroradicals ending with styrene and methyl methacrylate monomer units.