The structure of lithium barium silicate, Li(2)BaSiO(4), has been determined from synchrotron radiation powder data. The title compound was synthesized by high-temperature solid-state reaction and crystallizes in the hexagonal space group P6(3)cm. It contains two Li atoms, one Ba atom (both site symmetry ..m on special position 6c), two Si atoms [on special positions 4b (site symmetry 3..) and 2a (site symmetry 3.m)] and four O atoms (one on general position 12d, and three on special positions 6c, 4b and 2a). The basic units of the structure are (Li(6)SiO(13))(5-) units, each comprising seven tetrahedra sharing edges and vertices. These basic units are connected by sharing corners parallel to [001] and through sharing (SiO(4))(4-) tetrahedra in (001). The relationship between the structures and luminescence properties of Li(2)SrSiO(4), Li(2)CaSiO(4) and the title compound is discussed.