The crystal structure of a synthetic NaAlSiO 4 modification has been solved and refined to an R index of 0.020 for 2745 independent reflections. The compound is hexagonal with space group symmetry P6 1 , a = 9.995(2) Aa and c = 24.797(4) Aa. The crystal showed twinning by merohedry according to m 210 , which was accounted for in the calculations. The phase was named trinepheline, following prior studies, because the length of its c lattice parameter is three times the length of the c parameter in nepheline, whereas the a parameter is about 10 Aa in both phases. The crystal structure is characterized by layers of six-membered tetrahedral rings of exclusively oval conformation. The rings are built up by regularly alternating AlO 4 and SiO 4 tetrahedra. The stacking of the layers parallel to the c axis results in a three-dimensional network containing channels that are occupied by the Na cations. Although structural similarities with respect to tridymite derivatives can be found, hexagonal trinepheline represents a new type of stuffed tridymite that is not a simple superstructure of nepheline.