High-resolution ESR spectra of the ground-state negative ions of hexafluorocyclopropane (c-C3F6center dot-), octafluorocyclobutane (c-C4F8center dot-), and decafluorocyclopentane (c-C5F10center dot-) are reported and their isotropic F-19 hyperfine coupling constants (hfcc) of 198.6 +/- 0.4 G, 147.6 +/- 0.4 G, and 117.9 +/- 0.4 G, respectively, are in inverse ratio to the total number of fluorine atoms per anion. Together with the small value of 5.2 +/- 0.4 G determined for the isotropic C-13 hfcc of c-C4F8center dot-, these results indicate that in each case the singly occupied molecular orbital (SOMO) is delocalized over the equivalent fluorines and possesses a nodal plane through the carbon atoms of a time-averaged D-nh structure. A series of quantum chemical computations were carried out to further characterize these anions and their neutral counterparts. Both the B3LYP density functional and second-order Moller-Plesset perturbation theory (MP2) indicate that c-C3F6center dot- adopts a D-3h geometry and a (2)A(2)(") ground electronic state, that c-C4F8center dot- adopts a D-4h geometry and a (2)A(2u) ground electronic state, and that c-C5F10center dot- adopts a C-s structure and a (2)A' electronic state. Moreover, the F-19 hyperfine coupling constants computed with the MP2 method and a high quality triple-zeta basis set are within 1% of the experimental values. Also, the values computed for the C-13 hfcc of CC4F8center dot- are consistent with the experimental value of 5.2 G. Therefore, in keeping with the ESR results, these negative ions derived from first-row elements can be characterized as pi(star) species. In addition, the hypervalency of these perfluorocycloalkane radical anions has been clarified.