Amphiphilic acrylic copolymers containing long aromatic side-chains with aromatic ester and 2-hydroxyethylacrylate (HEA) spacers were investigated by temperature-resolved pyrolysis-field ionization mass spectrometry. The degradation products strongly depend on the heating rate, which ranged from 0.2 to 1.2 K s −1. In an initial thermal degradation step, hydroxyl groups of the HEA side-groups react with the aromatic ester bonds in the long side-chains forming a volatile phenol derivative. At higher temperatures, especially using the high heating rate 1.2 K s −1, olefin formation via cis-elimination occurs at the acrylic ester bonds. This reaction results in the formation of carboxylic acid groups in the polymer backbone. Subsequently, these acids react with both the aromatic and the acrylic ester groups of the long side-chains. At temperatures above 400°C this crosslinked residue decomposes to form secondary pyrolysates via cis-elimination and ester exchange reactions.