The title compound has been prepared by hydrothermal synthesis and its crystal structure was determined by single crystal X-ray diffraction: space group I4/mmm, a=6.3856(2), c=10.6119(9)<space>Å, wR 2 =0.039, R=0.016. The crystal structure of Na 3 {V 2 O 2 F[PO 4 ] 2 } is formed by layers of alternating [VO 5 F] octahedra and [PO 4 ] tetrahedra sharing O vertices parallel to the ab plane. Along the c direction the V octahedra are joined pairwise through common F vertices in the inversion centres. The sixth O vertex of the V octahedron is the terminal oxo ligand of a vanadyl group. Thus, the structure is described by a mixed paraframework of octahedra and tetrahedra {V 2 O 2 F[PO 4 ] 2 } ~ ~ ~ with disordered Na atoms in the interstices. The new phase is discussed as a member in the row of compounds structurally related to the mineral natisite and VOPO 4 .2H 2 O.