The new compounds, Sr6Sb6S17, BA(2.62)Pb(1.38)Sb(4)S(10), and Ba3Sb4.66S10 were prepared by the molten polychalcogenide salt method. Sr6Sb6S17 crystallizes in the orthorhombic space group P2(1)2(1)2(1) with a 8.2871(9) Angstrom, b = 15.352(2) Angstrom, c = 22.873(3) Angstrom, and Z = 4. This compound presents a new structure type composed of [Sb3S7](5-) units and trisulfide groups, (S-3)(2-), held together by Sr2+ ions. The [Sb3S7](5-) fragment is formed from three corner-sharing SbS3 trigonal pyramids. The trisulfide groups are separated from the [Sb3S7](5-) unit and embedded between the Sr2+ ions. Ba3Sb4.66S10 and Ba2.62Pb1.38Sb4S10 are not isostructural but are closely related to the known mineral sulfosalts of the rathite group. Ba3Sb4.67S10 is monoclinic P2(1)/c with a = 8.955(2) Angstrom, b = 8.225(2) Angstrom, c = 26.756(5) Angstrom, beta = 100.29(3)degrees and Z = 4. Ba-2.62Pb1.38Sb4S10 is monoclinic P2(1) with a = 8.8402(2) Angstrom, b = 8.2038(2) Angstrom, c = 26.7623(6) Angstrom, beta = 99.488(1)degrees and Z = 4. The Sb atoms are stabilized in SbS3 trigonal pyramids that share corners to build ribbonlike slabs, which are stitched by Ba/Pb atoms to form layers perpendicular to the c-axis. These materials are semiconductors apd show optical band gaps of 2.10, 2.14, and 1.64 eV for Sr6Sb6S17, Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10, respectively. Raman spectroscopic characterization is reported. Sr6Sb6S17; Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10 melt congruently at 729, 770, and 749 degreesC, respectively.