A consecutive radical addition-coupling reaction involving dithioester is applied to produce thermodegradable multisegmented polymer using a,?-dibromo polymer as precursor. The macroradical generated by single electron transfer process promoted by Cu/ligand from a,?-dibromo polymer can efficiently add to ethyl dithiobenzoate, which results intermediate adduct radical. The in situ formed adduct radical immediately undergoes crosscoupling reaction with macroradical, generating segmented polymer bridged with C?S bond. The consecutive radical addition-coupling reaction generates multisegmented polymer linked by C?S bond following step-growth mechanism. The multisegmented polymer can be thermodegraded in the presence of hydrogen atom donor or air. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012