The thermal degradation mechanisms of amphiphilic acrylic copolymers containing mesogenic pyrimidine side chains and hydrophilic 2-hydroxyethyl acrylate (HEA) main-chain spacer units were investigated by thermogravimetry (TG) and pyrolysis-field ionization mass spectrometry (Py-FIMS). The degradation behaviour of these polymers depends on the amount of HEA incorporated. Thermogravimetry revealed that the main decomposition occurs in a single step for the pyrimidine homopolymer, whereas with increasing HEA content a two-step process evolves. The major products identified by Py-FIMS are two alcohols and one olefin split from the aromatic side chains. Depolymerization is only a minor degradati…