Single crystals of NaBaVS 4 were grown by precipitation from a sodium polysulfide flux at temperatures below 350°C. The compound crystallizes in the centrosymmetric monoclinic space group P2 1 /n, with four formula units per unit cell. The unit cell dimensions are a=6.143(12) A ̊, b=9.480(2) A ̊, c=11.667(2) A ̊ and β=102.149(14)°. The V 5+ cations are surrounded by a tetrahedron of sulfide anions, the Ba 2+ cations are coordinated by nine sulfides in a distorted tricapped trigonal prismatic array, and the Na + cations, which are disordered, are surrounded by seven sulfide ions. Conductivity and magnetic susceptibility studies of a single crystal show that it is a non-magnetic insulator, which suggests that it is a normal valence compound.