Abstract: | New decavanadate minerals, the products of the leaching or metasomatic processes, are possible in nature via Na/Rb removal/inclusion reactions. As part of our search for novel vanadate phases with varying functionalities, a new phase, tetrarubidium hexaaquasodium hydrogen decavanadate tetrahydrate, Rb4Na(H2O)6]HV10O28]·4H2O, has been synthesized by the hydrothermal technique at 553 K. Ten shared edges of V‐centred octahedra form monoprotonated decavanadate cages, which are joined together via hydrogen bonds into one‐dimensional chains parallel to the 101] direction. Within these chains, H atoms are sandwiched between neighbouring polyanions. Na and Rb atoms and H2O molecules occupy interstices flanked by the anionic chains providing additional crosslinking in the structure. This compound is the second decavanadate with P2/n symmetry. Structural relationships among protonated and deprotonated decavanadates with inorganic cations, including minerals of the pascoite group, are discussed. |