NaSm(PO3)4 has been prepared by solid state reactions. It belongs to type II of the structural family of M
I
Ln
III(PO3)4 compounds (M
I = alkali metal and Ln
III = rare earth metal) and is composed of ∞(PO3)n]n− polyphosphate chains with a repeating unit of four PO4 tetrahedra. The chains extend parallel to [100] and share O atoms with irregular SmO8 polyhedra, forming a three-dimensional framework which delimits tunnels occupied by Na+ cations in a distorted octahedral environment