Herein, we demonstrate that the chain-initiating dissociation of cyclohexyl hydroperoxide, CyOOH, is substantially accelerated by H-bond acceptors (e.g. Teflon), which assist O-O bond breaking by stabilising the leaving OH radical. This is a completely new approach to boost the chain-propagating radical concentration. Indeed, up to now, literature has remained focussed on transition metal catalysis. In addition to this initiation effect, we demonstrate how inert perfluorinated compounds are also able to steer the selectivity at the molecular level, by promoting the conversion of the intermediate cyclohexyl hydroperoxide to the most desired end-product, cyclohexanone. This effect is explained by an enhanced, H-bond-assisted, hydroperoxide propagation. This hitherto overlooked hydroperoxide propagation was recently presented by us as the dominant cyclohexanone and cyclohexanol source. We herein thus confirm our previously reported autoxidation scheme, and illustrate its usefulness as a solid basis for designing new catalytic systems.