Bis(phenylthio)methane (L1) reacts with CuI to yield the 1D-coordination polymer [{Cu 4 (μ 3 -I) 4 }(μ-L1) 2 ] n (1) bearing cubane Cu 4 I 4 clusters as connecting nodes. The crystal structures at 115, 155, 195, and 235 K provided evidence for a phase transition changing from the monoclinic space group C2/c to P2 1 /c. The self-assembly process of CuI with bis(p-tolylthio)methane (L2), bis(4-methoxyphenylthio)methane (L3), and bis(4-bromophenylthio)methane (L4) affords the 1D-coordination polymers [{Cu 4 (μ 3 -I) 4 }(μ-Lx) 2 ] n (x = 2, 3, or 4). Compounds 2 and 4 are isostructural with C2/c low temperature polymorph of 1, whereas the inversion centers and 2-fold axes are lost in 3 (space group Cc). The use of bis(m-tolylthio)methane (L5) has no impact on the composition and overall topology of the resulting 1D ribbon of [{Cu 4 (μ 3 -I) 4 }(μ-L5) 2 ] n (5). Even the coordination of the sterically crowded dithioether bis(5-tert-butyl-2-methylphenylthio)methane (L8) does not alter the network topology generating the 1D polymer [{Cu 4 (μ 3 -I) 4 }(μ-L8) 2 ] n (8). The 1D polymer [{Cu(μ 2 -Br) 2 Cu}(L1) 2 ] (9) results from the coordination of L1 with CuBr in a 1:1 metal-to-ligand ratio. In contrast to the mean Cu•••Cu distances, which are <2.8 Å noted for the Cu 4 (μ 3 -I) 4 clusters in the 1D polymers 1−8, the Cu•••Cu contact within the Cu(μ 2 -Br) 2 Cu rhomboids of 9 [2.9194(8) Å] is above the sum of the van der Waals radii of two Cu atoms. The structural arrangement of 1D polymer [{Cu(μ 2 -Br) 2 Cu}(L3) 2 ] n (11) is quite similar to that of 9. While the reaction of CuBr with L5 results in a similar 1D polymer [{Cu(μ 2 -Br) 2 Cu}(L5) 2 ] n (12), the reaction of CuBr with L2 leads to the dinuclear complex [{Cu(μ 2 -Br) 2 Cu}(η 1 -L2) 4 ] (10) ligated by four pendent bis(p-tolylthio)methane ligands. The ligation of bis(o-tolylthio)methane, L6, on CuBr also yields a discrete complex [{Cu(μ 2 -Br) 2 Cu}(MeCN) 2 (η 1 -L6) 2 ] (13) bearing MeCN and dangling dithioether ligands. A strong luminescence is detected for all CuI polymers, all exhibiting emission lifetimes in the microsecond time scale (i.e., phosphorescence). The polymers containing the Cu 4 I 4 core (1−8) exhibit the typically observed low-energy band and sometimes a weaker high-energy band. The nature of the low-energy band was proposed based on literature DFT and TDDFT computations and is predicted to be a mixture of cluster-centered (CC*) and metal/halide-to-ligand charger transfer (M/XLCT). An approximate relationship between the Cu•••Cu distance and the emission maxima corroborates the CC* contribution to the nature of the excited states. The emission of the rhomboid-containing materials is assigned to M/XLCT based on literature works on similar motifs.