The dehydrated zeolites LiX-1.0 [(SiAlO4)(96)Li-96], LiX-1.25 [(Si106Al86O384)Li-86], LiA [(SiAlO4)(96)Li-96], and LiA-1.15 [(Si102.7Al89.3O384)Li-89.3] have been studied in a vacuum and in the presence of oxygen and nitrogen gases by Li-7 and Li-6 MAS NMR spectroscopy. The adsorption of Nz molecules causes a small shift (Delta delta = 0.2 ppm) to higher frequencies for the component belonging to cations interacting with Nz molecules. In contrast, the adsorption of oxygen causes a strong downfield (paramagnetic) shift depending on the accessibility of the Li cations. Observations made in the Li-7 MAS NMR spectra recorded at the different conditions were used to propose a model for the location of the Li cations in zeolite LiA. As determined from the NMR spectra, the difference in nitrogen adsorption capacity of LiX and LiA is directly related to the accessibility of Li cations in each material.