NaSbS2 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Na1+ is bonded to six equivalent S2- atoms to form a mixture of corner and edge-sharing NaS6 octahedra. The corner-sharing octahedral tilt angles are 11°. There are a spread of Na–S bond distances ranging from 2.93–2.99 Å. Sb3+ is bonded in a rectangular see-saw-like geometry to four equivalent S2- atoms. There are two shorter (2.48 Å) and two longer (2.79 Å) Sb–S bond lengths. S2- is bonded to three equivalent Na1+ and two equivalent Sb3+ atoms to form a mixture of corner and edge-sharing SNa3Sb2 square pyramids.