The cyclization reactions of the 4-pentenyl, 5-hexenyl, 6-heptenyl, and 7-octenyl fluorinated and ether radicals have been studied by a hybrid Hartree-Fock density functional method. The reliability of this approach has been confirmed in agreement with experimental data and post-Hartree-Fock projected Møller-Plesset second-order method. The analysis of the theoretical results shows that two factors are crucial for the determination of the regiochemistry and the reactivity of these reactions. The first factor is the ability of the starting radical to have a stable conformation in position to form the transition state, and the second one is the enthalpic effect of the reaction through the stability of the resulting cyclized radical. It should be pointed out that these factors are not linked to the polarity of the radicals due to the presence of CF2 groups.