Five barium tantalum sulphides have been prepared by sulphurization of mixtures of BaCO₃ and Ta₂O₅ in a CS₂ atmosphere. They are (A) BaTa₂S₅, hexagonal a = 3.326, c = 25.21 A (B) Ba₃Ta₂S₈, monoclinic a = 12.616, b = 6.850, c = 11.957A β = 108.94°, (C) Ba_16.5 Ta₉ S₃₉, rhombohedral a = 6.883; c = 41.83 A in hexagonal setting, (D) Ba₂TaS₅, hexagonal a = 6.926, c = 49.43A, and (E) Ba₉Ta₄S₂₀, hexagonal a = 6.959, c = 21.5586A. Their crystal structures, except for that of (A) BaTa₂S₅, were determined by refinement with powder X-ray diffraction data, by means of Rietveld method revealing that the structures are analogous with each other and close to that of BaTaS₃.