Na-23 MAS NMR and synchrotron X-ray powder diffraction methods have been used to study the binding of hydrofluorocarbon-134 (HFC-154, CF2HCF2H) in zeolite NaY. A contraction of the volume of the unit cell is observed on gas adsorption, and the interaction of HFC-134 with the extraframework sodium cations is so strong that extraframework sodium cations in the sodalite cages (site I’) migrate into the supercages. These sodium cations are found on positions close to the site III’ positions of zeolite NaX. Both ends of the HFC molecules are bound to sodium cations, the HFC molecule bridging the site II and III’ cations in the supercages. The strong cation-HFC interaction results in a considerable displacement of the sodium site II cation along the [111] direction into the supercage and an increase in the T-O-T bond angle for the three oxygen atoms coordinated to this cation. A decrease in the Na-23 quadrupole coupling constant on HFC adsorption from 4.4 to less than 2.8 MHz, for the sodium cations originally located in the sodalite cages (site I’), is consistent with the sodium cation migrations.