The principal values of the19F hyperfine tensor for the ·CF(CONH2)2radical in aγ-irradiated single crystal of difluoromalonamide have been determined to be 200, -1, -10gperpendicular to the radical plane, parallel to the C-F bond, and perpendicular to the C-F bond in the radical plane, respectively. The deviation from axial symmetry of the hyperfine tensor is discussed in comparison with that in other related compounds and it is concluded that the spin polarization of 2pσelectrons in the C-F bond plays an important role. The polarization factors,QcffandQfcf, for the 2pσelectrons have been estimated to be -45 and +233gso as to account for the hyperfine tensors of a series of compounds.