A novel precursor to the distonic O- and C-centered radical cations Oxo(+)O and Oxo(+)C was designed and synthesized, which represents model systems for radicals produced during polyester degradation. The precursor is equipped with a nitrate functional group, which serves as a masked site for these alkoxyl and carbon radicals that are unleashed through collision-induced dissociation (CID). Oxo(+)O and Oxo+C feature a cyclic carboxonium ion as permanent charge tag to enable monitoring their ion-molecule reactions on the millisecond to second time scale in the ion trap of the mass spectrometer. The reactions of Oxo(+)O and Oxo(+)C with cyclohexene, cyclohexadiene, ethyl acetate, 1,1-dimethoxyethane, and 1,2-dimethoxyethane, which exhibit structural features present in both intact and defective polyesters, were explored through product and kinetic studies to identify "hot spots" for radical-induced damage in polyesters. All reactions with Oxo(+)O were extremely fast and proceeded predominantly through HAT. Oxo(+)C was about two orders of magnitude less reactive and did not noticeably damage aliphatic ester moieties through hydrogen abstraction on the time scale of our experiments. Radical addition to alkene pi systems was identified as an important pathway for C-radicals, which needs to be included in polymer degradation mechanisms.