The synthesis, structure, and properties of (Et4N)4Nb2S4(NCS)8 (1), (EtQuin)4Nb2S4(NCS)8 (1a), Nb2S4(Et2-NCS2)4 (2), Nb2S4(ROCS2)4 (3, R = Et, (i)Pr, Cy), and Nb2S4(((i)PrO2PS2)4 (4) are described. Complexes 1 and 1a have been obtained by fusing together NbS2Cl2 and KNCS, dissolving this melt in water, and adding corresponding organic cations. Complex 1a crystallizes in the P1BAR space group with the following unit cell dimensions : a = 10.553(2) angstrom, b = 11.773(2) angstrom, c = 13.440(2) angstrom, alpha = 97.18(1)-degrees, beta = 103.66(1)-degrees, gamma = 105.49(1)-degrees, and Z = 1. A total of 2060 reflections with F > 6sigma(F) were employed, and the structure solution was refined to the values of conventional indices R and R(W) 0.057 and 0.055, respectively. The anion of 1 has eight-coordinated Nb atoms ligated by eta2:eta2:mu2 ligands and eight terminal isothiocyanate ligands. The Nb-Nb distance is 2.913(2) A. The NCS ligands in 1 and 1a can be easily replaced with bidentate 1,1-dithioacid ligands to yield the complexes 2-4. Complex 4 crystallizes in P1BAR space group with the following unit cell dimensions : a = 8.925(2) angstrom, b = 10.349(1) angstrom, c = 14.161(2) angstrom, a = 81.57(1)-degrees, beta = 107.77(1)-degrees, gamma = 98.98(1)-degrees, and Z = 1. A total of 1932 reflections with F>4sigma(F) were employed, and the structure solution was refined to the values of conventional indices R and R(W) 0.030 and 0.028, respectively. Just like 1a, complex 4 has a Nb2S4 core. The Nb-Nb distance is 2.898(1) angstrom. Each Nb atom, in addition, is coordinated by two chelating dithiophosphate ligands. Mass spectra of 2 and 4 have been studied. Complex 2 is oxidized by Fc+ giving paramagnetic cluster cation [2]+.