Treatment of [Et4N][Tp*WS3] (1) (Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate) with 2 equiv of AgSCN in MeCN afforded a novel neutral compound [(Tp*WS2)(2)(mu-S-2)] (2). Reactions of 2 with excess CuX (X = Cl, Br, I) in MeCN and CH2Cl2 or CHCl3 formed three neutral W/Cu/S clusters [{Tp*W(mu(3)-S)(3)Cu-3(mu-Cl)}(2)Cu(mu-Cl)(2)(mu(7)-Cl)(MeCN)](2) (3) [{TP*W(mu(3)-S)(3)Cu-3}(2)Br(mu-Br)(2)(mu(4)-Br)(MeCN)] (4), and [{Tp*W(mu(3)-S)(3)Cu-3}(2){Cu-2(mu-I)(4)(mu(3)-I)(2)}] (5), respectively. On the other hand, treatment of 2 with CuX (X = Cl, Br) in the presence of Et4NX (X = CI, Br) produced two anionic W/Cu/S clusters [Et4N] [{Tp*W(mu(3)-S)(3)Cu3X}(2) (mu-X)(2)(mu(4)-X)] (6: X = Cl; 7 X = Br). Compounds 2-7 were characterized by elemental analysis, IR. UV-vis, H-1 NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray crystallography. The dimeric structure of 2 can be viewed as two [Tp*WS2] fragments in which two W atoms are connected by one S-2(2-) dianion. Compounds 3-7 all possess unique halide-bridged double cubanelike frameworks. For 3, two [Tp*W(mu(3)-S)(3)Cu-3](2+) dications are linked via a mu(7)-Cl- bridge, two mu-Cl- bridges, and a [Cu(MeCN)(mu-Cl)(2)](+) bridge. For 4, one [Tp*W(mu(3)-S)(3)Cu-3(MeCN)](2+) dication and one [Tp*W(mu(3)-S)(3)Cu3Br](+) cation are linked via a mu(4)-Br- and two n-Br bridges. For 5, the two [Tp*W(mu(3)-S)(3)Cu-3](2+) dications are bridged by a linear [(mu-I)(2)Cu(mu(3)-I)(2)Cu(mu-I)(2)](4+) species. For 6 and 7, two [Tp*W(mu(3)-S)(3)Cu3X](+) cations are linked by a mu(4)-X- and two mu-X- bridges (X = Cl, Br). In addition, the third-order nonlinear optical (NLO) properties of 2-7 in MeCN/CH2Cl2 were investigated by using femtosecond degenerate four-wave mixing (DFWM) technique.