A sample of the zeolite paulingite from the locality Vinarická Hora was investigated by means of chemical, thermal, powder and single crystal X-ray methods. The fully transparent, colourless to pale yellow crystals exhibit the form {110} and occur together with phillipsite. The chemical composition is (Ca_2.57K_2.28Ba_1.39Na_0.38)(Al_11.55Si_30.59O₈₄)·27H₂O, Z = 16 with minor amounts of Mg (<0.05), Sr (<0.13), Mn (<0.01), and Fe (<0.04). The chemical differences from previously described paulingites are a high Ba-content, a lower Si/(Al+Fe) ratio of 2.64, and a reduced water-content. The calculated density is 2.098 g cm⁻³, and the observed refractive index is 1.482(2). The dehydration behaviour is characterized by a main weight loss from 24–190°C (−11.2 wt.%, ≅ 21H₂O) and a minor weight loss from 190–390°C (−3.1 wt.%, ≅ 6H₂O). The rehydration capability was proven up to 150°C. The dehydration process during the main weight loss is accompanied by a reduction of the cell volume of 11%. The refined lattice parameters of the X-ray powder data are a a = 35.1231 (5) Å and a = 33.7485(8) Å of an untreated and a dehydrated sample, respectively. A breakdown of the paulingite structure can be observed while the remaining water content decomposes. The single crystal X-ray refinement of this chemically different sample material derived three main cation positions, which are inside a so called paulingite or π-cage (Ca), between 8-rings of neighbouring π-cages (Ba), and in the centre of the non-planar 8-rings of the γ-cage (K). Further partially occupied cation positions (Ca,Na) were located in the planar 8-rings of the α- and γ-cages. No positions within the double 8-membered rings were detected. The water is localized around the main cation positions and in three clusters of partially occupied sites.