Homopolymers and copolymers of styrene and different acrylic esters (i.e., acrylates) were synthesized by the free-radical solution polymerization technique. Feed ratios of the monomers styrene and cyclohexyl acrylate/benzyl acrylate were 90 : 10, 75 : 25, 60 : 40, 50 : 50, 40 : 60 and 20 : 80 (v/v) in the synthesis of copolymers. All 6 homopolymerizations of acrylic ester synthesis were carried out in N,N(dimethyl formamide) except for the synthesis of poly(cyclohexyl acrylate) (PCA), where the medium was 1,4-dioxane. Benzoyl peroxide (BPO) and azobisisobutyronitrile (AIBN) were used as initiators. The polymers synthesized were characterized by FTIR, H-1-NMR, C-13-NMR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and viscosity measurements. The reactivity ratios were determined by the Fineman-Ross method using H-1-NMR spectroscopic data. The reactivity ratios (r) for the copolymerization of styrene (r(S)) with cyclohexyl acrylate (r(CA)) were found to be r(S) = 0.930 and r(CA) = 0.771, while for the copolymerization of styrene with benzyl acrylate, the ratios were found to be r(S) = 0.755 and r(BA) = 0.104, respectively. The activation energies of decomposition (E-a) and glass-transition temperature (T-g) for various homo- and copolymers were evaluated using TGA and DSC analysis. The activation parameters of the viscous flow, voluminosity (V-E) and shape factor (nu) were also computed for all systems using viscosity data.