Dielectric relaxation properties of dehydrated and hydrated Na-mordenite are measured by means of thermally stimulated depolarization current (TSDC) spectroscopy. TSDC spectroscopy allows us to determine two characteristic terms which depend on the hydration state: on one hand, the site selectivity of sodium ions and water molecules and on the other hand, the sodium/network interaction energy. Upon hydration, half of the Na+ ions remain embedded in site A, whereas the other Na. ions are extracted from the main channel sites (sites D and E). Besides, according to the water content, we show that water molecules are adsorbed in different sites, first in sites H or F. then in sites B, C, or G, and finally in sites G. Furthermore, it is pointed out that the interaction energy (Na+/zeolite) value depends on the sodium localization following the sequence: E-site A > E-site (D) > E-site (E). Finally, it is shown that the interaction energy decreases as the water content increases (typically from 0.79 eV to 0.44 eV). This evolution is successfully described by using a qualitative model referring to electronegativity and charge-transfer concepts.