AbstractKinetics of product accumulation during the oxidative decarboxylation of cyclohexane monocarboxylic acid has been followed by GCMS, inhibitor and chemiluminescence methods. Results indicate that in the degenerate branching chain process selective (peroxy) radicals abstract predominantly tertiary hydrogen atoms from the substrate while non‐selective (e.g. hydroxyl, alkoxy) radicals attack also secondary hydrogen atoms. The rate constant of the chain propagation was found to bekp= 7.5×106exp(‐57.6kJmol−1/RT) 1mol−1s−1. Furthermore it has been established, that the oxidative decarboxylation proceeds via two parallel pathways: one resulting in cyclohexanone, while the other avoiding the formation of