α-l-Sorbose single crystals were X-irradiated at 295 K (room temperature). A combined electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and ENDOR-induced EPR (EI-EPR) study at 120 K revealed a realm of radiation-induced free radicals in this sugar system. In the present work, a pair of closely related radicals is focused on, being dominant immediately after irradiation, but unstable with respect to long time storage or upon warming the samples. A density functional theory (DFT) study was carried out considering the complete hyperfine coupling tensors (principal axes and anisotropic and isotropic couplings) in comparison with the observed electron−proton interactions. This combined approach yielded very plausible models for both radicals, which are formed by a net hydrogen-abstraction from the C3 position of the six-membered sorbose ring. It appears that the difference between the two species is linked to the molecular disorder in the sorbose crystal structure. In addition, DFT calculations of the g tensors were performed for the plausible radical conformations.