This investigation reports a comparative study of poly(2-ethylhexyl acrylate) (PEHA) prepared via atom transfer radical polymerization (ATRP), reverse atom transfer radical polymerization (RATRP) and conventional free radical polymerization (FRP). The molecular weights and the molecular weight distributions of the polymers were measured by gel permeation chromatography (GPC) analysis. Structural characterization of the polymers was carried out by ¹H NMR and MALDI-TOF-MS analyses. Thermal properties of the polymers were evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The polymerization results and the thermal properties of PEHAs prepared via ATRP, RATRP and FRP were compared.