The crystal structure of the title compound, [NaNd(C8H11NO5PS)4]n, is composed of two types of crystallographically independent polymeric chains, A and B, respectively, which are formed by alternating anions and sodium cations. In both polymeric chains, NdIII ions are eight-coordinated by O atoms belonging to the sulfonyl and phosphoryl groups of four bidentate chelate ligands. In chain A, the coordination polyhedron of the NdIII ion has a conformation intermediate between bicapped trigonal-prismatic and square-antiprismatic, and the NaI ion is coordinated by two N and four O atoms in a distorted octahedral geometry. In chain B, the coordination polyhedron of Nd is a slightly distorted square antiprism, and Na is coordinated by four O atoms in a distorted tetrahedral geometry.