Potassium sodium metavanadate, KNa(VO3)2, crystallizes with the pyroxene structure and is made up of VO4 tetrahedral chains, NaO6 octahedra and KO8 dodecahedra. The chains of corner-sharing VO4 tetrahedra are crosslinked through the NaO6 octahedra and KO8 dodecahedra to form a three-dimensional structure with the K+ and Na+ cations, which lie on twofold axes, situated in the void space. The coordination around the Na+ ion is close to normal octahedral, while the O atoms coordinated to the K+ ion are arranged approximately in a dodecahedral fashion.