The ESR spectrum of the chain-end radical RCF2CF2 center dot detected in Nafion perfluorinated membranes exposed to the photo-Fenton reagent was accurately simulated by an automatic fitting procedure, using as input the hyperfine coupling tensors of the two F-alpha and two F-beta nuclei as well as the corresponding directions of the principal values from density functional theory (DFT) calculations. An accurate fit was obtained only for different orientations of the hyperfine coupling tensors for the two F-alpha nuclei, indicating a nonplanar structure about the C-alpha radical center. The fitted isotropic hyperfine splittings for the two F-beta nuclei in the Nafion radical, 24.9 and 27.5 G, are significantly larger than those for the chain-end radical in Teflon (15 G), implying different radical conformations in the two systems. The excellent fit indicated that the geometry and electronic structure of free radicals can be obtained not only from single-crystal ESR spectroscopy, but also, in certain cases, from powder spectra, by combination with data from DFT calculations. The optimized structures obtained by DFT calculations for the CF3CF2CF2CF2 center dot or CF3OCF2CF2 center dot radicals as models provided additional support for the pyramidal structure determined from the spectral fit. Comparison and analysis of calculated and fitted values for the hyperfine splittings of the two F-beta nuclei suggested that the radical detected by ESR in Nafion is ROCF2CF2 center dot, which originates from attack of oxygen radicals on the Nafion side chain. The combination of spectrum fitting and DFT is considered important in terms of understanding the hyperfine splittings from F-19 nuclei and the different conformations of fluorinated chain-end-type radicals RCF2CF2 center dot in different systems, and also for elucidating the mechanism of Nafion fragmentation when exposed to oxygen radicals in fuel cell conditions.