The structure of NaZr2(AsO4)(3), which belongs to the Nasicon-type family, was solved by the Rietveld method in the R(3) over bar c space group, from X-ray powder diffraction data. The hexagonal unit cell parameters are a(h) = 9.1518(2) Angstrom and c(h) = 23.1097(4) Angstrom. The structure is formed by a three-dimensional network of AsO4 tetrahedra and ZrO6 octahedra sharing corners. Na atoms occupy totally the M1 site. Raman and infrared spectra were recorded and assignments of the As-O stretching and bending modes were made. (C) 2003 Elsevier Ltd. All rights reserved.