In the context of a detailed investigation of the luminescent properties of Na1-xAgxZn(PO3)(3) (0 < x 1) compounds, the structure of the orthorhombic form of sodium-zinc phosphate was confirmed and resolved by the Rietveld profilation method. The cell is orthorhombic (S.G. Pbca), with a = 14.259(2), b = 14,234(3), and c = 14.238(4) Angstrom. The structure is characterized by long phosphate chains connected to infinite chains of [NaO6] and [ZnO6] polyhedra sharing faces. When doped with silver ions, two luminescences have been observed. The UV emission is well known as typical of isolated Ag+ ions. The visible emission, interpreted in the most cases in the term of d(10)-d(10) interactions, originates probably from a silver-zinc association.