Abstract The quenching of the triplet states of several model αβ‐unsaturated ketones and that produced by thermal oxidation of polybutadiene by the triplet quencher cyclooctadiene at low temperatures has been studied by quantum yield and phosphorescence decay‐time methods. Both the Perrin and Inokuti–Hirayama relationships were tested and a typical exchange interaction distance for half‐quenching of R0 = 12 ± 1 Å was obtained for both models on all compounds studied.