Cs-133 hyperfine sublevel correlation (HYSCORE) spectroscopy has been employed to characterize the structure of adsorption complexes of di-tert-butyl nitroxide (DTBN) with cesium cations in zeolite CsNaY. The experimental Cs-133 HYSCORE data proved the direct coordination of the adsorbed DTBN molecules to the Cs+ ions and revealed nonambiguously the existence of two different types of adsorption complexes. Evaluation of the orientation selective Cs-133 HYSCORE spectra provided the Cs-133 hyperfine coupling tensors and thus information about the geometrical structure of those complexes. For one type of adsorption complexes, a complex geometry was obtained where the Cs+ ion is located within the molecular mirror plane of the DTBN radical with an oxygen-cesium cation bond length of 0.25 nm. For this, the isotropic Cs-133 hyperfine coupling was negative. The second Cs+-DTBN complex is characterized by a bent structure. With an isotropic Cs-133 hyperfine coupling of 9 MHz, the unpaired electron spin density in this Cs+-DTBN complex localized at the Cs ion was 0.36%.