© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Poly(2-ethylhexyl acrylate) is synthesized by conventional radical bulk polymerization both with and without 1-dodecane thiol as chain transfer agent (CTA) at temperatures from 4 to 140 °C. Electrospray-ionization mass spectrometry is used to analyze the polymer. This reveals the occurrence of significant β-scission at high temperature and confirms the presence of CTA-capped polymers at all temperatures, as well as combination products from 4 to 65 °C. Subsequent 13 C melt-state NMR analysis allows quantification of branching and β-scission. Both are reduced when CTA is present, consistent with a "patching" effect. As expected, the amounts of β-scission and branching increase with synthesis temperature, although β-scission dominates at the highest temperature. The backbiting rate coefficient of 2-ethylhexyl acrylate is determined from NMR results, taking β-scission into account for the first time. Remarkable agreement with literature k bb values is obtained, especially for activation energy. This strongly suggests family-type behavior for acrylate k bb .