The construction of a new set of [(eta(5)-C5Me5)MoS3Cu3+based supramolecular compounds with different one-dimensional (1D) arrays from two preformed clusters [PPh4][(eta(5)-C5Me5)MoS3(CuX)(3)] (X = Br (1a), NCS (1b)) with 1,2-bis(4-pyridyl)ethane (bpe) and 1,3-bis(4-pyridyl)propane (bpp) is presented. Reactions of 1a with bpe in different molar ratios afforded {[{(eta(5)-C5Me5)MoS3Cu3}(2)(mu-bpe)(3.5)Br-4]center dot MeCN}(n) (2), {[{(eta(5)-C5Me5)MoS3Cu3}(2)(mu-bpe)(3)Br-4]center dot Sol}(n) (3a: Sol = DMSO center dot 3MeCN; 3b: Sol = 2aniline center dot 3MeCN), {[{(eta(5)-C5Me5)MoS3Cu3}(2)(mu-bpe)(3)(bpe)Br-4]center dot 0.35DMF}(n) (4), and {[{(eta(5)-C5Me5)MoS3Cu3)(2)(mu-bpe)(2)(mu-Br)(mu(3)-Br)Br-2]center dot DMF center dot MeCN}(n) (5). On the other hand, treatment of 1a or 1b with bpp produced [(eta(5)-C5Me5)MoS3Cu3(mu-bpp)(mu-Br)Br](n) (6) and {[{(eta(5)-C5Me5)MoS3Cu3}(2)(mu-bpp)(3)(mu-NCS)(2)(NCS)](NCS)}(n) (7). Compounds 2-7 have been characterized by elemental analysis, UV-vis spectroscopy, IR spectroscopy, H-1 NMR, and X-ray analysis. In 2, each [(eta(5)-C5Me5)MoS3Cu3] core serves as an angular two-connecting node to link other equivalent cores by single and double bpe bridges to form a 1D "Great Wall"-like chain. In 3a and 3b, the [(eta(5)-C5Me5)MoS3Cu3] cores are linked alternatively by single and double bpe bridges to give a 1D zigzag chain. In 4, six cluster cores (two as a two-connecting node and four as a three-connecting node) are connected by four single bpe and two double bpe bridges to form a cyclohexane-shaped repeating unit, which is further fused with other units to generate a 1D double-stranded chain. Compound 5 has a simple 1D zigzag chain consisting of the cluster cores linked by single bpe bridges. In 6, the cluster cores are linked by single bpp bridges to give a 1D helical chain, which further holds two symmetry-related chains through C - H center dot center dot center dot Br hydrogen-bonding interactions, thereby forming a 1D H-bonded triple-stranded chain. Compound 7 has a rare 1D quadruple chain, in which the [(eta(5)-C5Me5)MoS3Cu3] cores work as planar four- and five-connecting nodes to interconnect other equivalent cores through single bpp bridges and single and double thiocyanate bridges. In addition, the third-order nonlinear optical properties of la, 2, 3a, and 4-7 in aniline were also investigated by using the Z-scan technique with a 4.5 ns pulse laser at 532 nm.