The cubic crystal structure of the title compound, [NaNd(C(14)H(21)N(3)O(5)PS)(4)](n), is composed of one-dimensional polymeric chains propagating in [100], built up from [Nd(C(14)H(21)N(3)O(5)PS)(4)](-) anions and sodium cations functioning as linkers. In the complex anion, the Nd(3+) ion has an eightfold coordination environment formed by the sulfonyl and phosphoryl O atoms of four bidentate chelating N-(dimorpholinophosphor-yl)benzene-sulfonamidate ligands: the resulting NdO(8) polyhedron can be described as inter-mediate between dodeca-hedral and square anti-prismatic. The sodium ion adopts an NaO(4) tetra-hedral geometry arising from four monodentate benzene-sulfonamidate ligands. The resulting crystal structure is unusual because it contains substantial voids (800 Å(3) per unit cell), within which there is no evidence of included solvent.