The syntheses and structures of [K(18-crown-6)]2[K(18-crown-6)(H2O)2]2[Nb6Cl12(CN)6] · 2CH3CN (1) and [(C6H5)4P]4[Nb6Cl12(NCS)6] · 0.94CH3OH (2), determined by X-ray single crystal diffraction, are reported. Crystal data: [K(18-crown-6)]2[K(18-crown-6)(H2O)2]2[Nb6Cl12(CN)6] · 2CH3CN: monoclinic, P21/n, a = 17.8240(9), b = 15.9395(8), c = 18.660(1) Å, β = 113.833(2)°, Z = 2; [(C6H5)4P]4[Nb6Cl12(NCS)6] · 0.94CH3OH: triclinic, $$ P\bar{1} $$ , a = 14.6239(3), b = 14.6237(5), c = 15.9831(3) Å, α = 113.482(1)°, β = 114.684(1)°, γ = 92.585(1)°, Z = 1. Both complexes contain [Nb6Cl12 Y 6]4− cluster anions with Y = CN and NCS, respectively, on all six cluster exo-positions. They have been prepared via ligand substitution in solution, starting from K4[Nb6Cl18], which was synthesized by a high temperature solid state reaction. Structural trends and spectroscopic properties are discussed and compared to related compounds reported previously in the literature.