[GRAPHICS] A product and time-resolved kinetic study on the reactivity of tertiary arylcarbinyloxyl radicals bearing a-cyclopropyl and a-cyclobutyl groups has been carried out. Both the 1-cyclopropyl-1-phenylethoxyl (1(.)) and alpha,alpha-dicyclopropylphenylmethoxyl (2(.)) radicals undergo beta-scission to give cyclopropyl phenyl ketone as the major or exclusive product with rate constants higher than that measured for the cumyloxyl radical. It is proposed that in the transition state for beta-scission of 1(.) and 2(.), formation of the C=O double bond is assisted by overlap with the C-C bonding orbitals of the cyclopropane ring. With tertiary arylcarbinyloxyl radicals bearing a-cyclobutyl groups such as the 1-cyclobutyl-1-phenylethoxyl (4(.)) and 1-cyclobutyl-1-phenylpropoxyl (5(.)) radicals, the fragmentation regioselectivity is essentially governed by the stability of the radical formed by P-scission. Accordingly, 4(.) undergoes exclusive C-cyclobutyl bond cleavage to give acetophenone, whereas with 5(.), competition between C-cyclobutyl and C-ethyl bond cleavage, leading to propiophenone and cyclobutylphenyl ketone in a 2:1 ratio, is observed.