Crystals of the title compound, NaScP(2)O(7), were grown by a flux method. The crystal structure is isotypic with those of α-NaTiP(2)O(7), NaYbP(2)O(7) and NaLuP(2)O(7), and is closely related to that of NaYP(2)O(7). The structural set-up consists of a three-dimensional framework of P(2)O(7) units that are corner-shared by ScO(6) octa-hedra, forming tunnels running parallel to [010]. The Na atoms are situated in the tunnels and are surrounded by nine O atoms in a distorted environment.