This article discusses thermal analysis of different molecular weight poly(2-ethylhexyl acrylates) synthesized by radical polymerization of 2-ethylhexyl acrylate. The main aim of this work was to investigate the thermal properties and degradation process of synthesized acrylic homopolymers and forming of thermal degradation products during their pyrolysis. As investigated method pyrolysis combined with gas chromatography was used. Poly(2-ethylhexyl acrylates) are used as plasticizers for pressure-sensitive adhesives applied in medical area.