Single crystals of the amino acid analogue hippuric acid, PhCONHCH2COOH, have been X-irradiated at 295 K and studied using X-band EPR, ENDOR, and ENDOR-induced EPR (EIE) spectroscopy at 295 and 130 K. Two different radical species were observed and characterized. The dominant species is radical R1, PhCONH-(CH2)-C-., supposedly formed by net decarboxylation from a pristine oxidation product. The nitrogen hyperfine and quadrupolar interactions yield information on the electronic structure in the nitrogen valence orbitals. The second radical species, radical R2, is formed by a net hydrogen addition to the phenyl entity of hippuric acid. As a reduction product, it may be formed by protonation of the negatively charged anion of the phenyl group, but the alternative mechanism of direct hydrogen addition to the phenyl ring cannot be ruled out. Spectral simulations indicate that radical R1 contributes about 85% of the total EPR spectrum, while the remaining 15% is contributed by radical R2.