The pulsed electron paramagnetic resonance (EPR) technique of hyperfine sublevel correlation spectroscopy (HYSCORE) was used to obtain structural information about vanadium(VO2+)-exchanged ZSM-5. HYSCORE spectra were obtained for vanadium-exchanged ZSM-5 before and after dehydration and after the adsorption of ammonia. For the hydrated samples, proton hyperfine coupling constants were measured and assigned to equatorial water ligands with orientations perpendicular and parallel to the equatorial plane. Nitrogen hyperfine coupling constants for adsorbed ammonia were also determined from the HYSCORE spectra. The results were compared with previous density functional theory (DFT) calculations of hyperfine coupling constants for vanadyl model complexes.