In the absence/presence of Ss, the one-pot assembly of [Et4N][Tp*WS3] [1; Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate] with [Cu(MeCN)(4)]PF6 and bis- or tetraphosphine ligands 1,2-bis-(diphenylphosphino) ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), and N,N,N',N'-tetrakis-(diphenylphosphinomethyl)ethylenediamine (dppeda) produces six W-Cu-S clusters, namely, [(Tp*WS3Cu2Cl)(2)(dppe)] (2), [Tp*WS3Cu4(dppp)(2)(mu(4)-Cl)(mu-Cl)]PF6 center dot MeCN (3 center dot MeCN), [(Tp*WS3Cu3)(2)(mu(4)-Cl)(mu-Cl)(2)(dpppS(2))] (4), [(Tp*WS3Cu2Cl)(2)(dppbS(2))]center dot 2MeCN center dot 2H(2)O (5 center dot 2MeCN center dot 2H(2)O), [(Tp*WS(3)Cu3Cl(2))(2)(dppbS(2))] (6), and [(Tp*WS3Cu3)(2)(Ph2PS2)(3)(mu(6)-Cl)(0.5)]-(PF6)(0.5)center dot 0.75CH(2)Cl(2) (7 center dot 0.75CH(2)Cl(2)). Compounds 2-7 are characterized by elemental analysis, IR, UV-vis, '1-I and 3113{1H} NMR, electrospray ionization mass spectrometry, and X-ray crystallography. For 2, the dppe ligand bridges a pair of butterfly-shaped [Tp*WS3Cu2] cores to form a double-butterfly-shaped structure. For 4, the dppp ligand is susceptible toward S association and forms an in situ generated dpppS2 ligand, supporting an octanuclear double-half-open-cubane structure and contrasting an analogous system wherein a pentanuclear motorcycle-shaped cationic cluster 3 is formed with the absence of S8. A longer dppb ligand readily converts to S-based ligands in 5 and 6, subsequently serving as bridges between a pair of a butterfly-shaped (5) and nest-shaped (6) clusters. Further use of a tetraphosphine ligand, dppeda, in the cluster formation, with the presence of S-8, leads to an unexpected ligand degradation to give the [Ph2PS2](-) anions. Three [Ph2PS2]-anions juxtapose a pair of nest-shaped cluster cores to yield an octanudear cluster, 7, featuring a cage to encapsulate mu(6)-Cl-. The third-order nonlinear-optical (NLO) properties of 2-7 in N,N-dimethylformamide, investigated using a Z-scan technique at 532 nm, show that 2-6 have a reverse saturable absorption, while 7 has a notable saturable absorption. All of 2-7 exhibit a self-focusing effect with hyperpolarizability y values in the range of 4.71 x 10(-3)0-1.02 x 10(-29) esu, which are 440-1000 times higher than that of 1. The formation of 4-7 from 1 through the in situ thiolation of phosphine ligands presents a new approach to the design and assembly of the W-Cu-S clusters with interesting structural arrays and better NLO properties.