A series of coordination polymers (CPs), some of them featuring an unusual architecture, have been constructed by treatment of RSCH 2 CCCH 2 SR (R = C 6 H 11 L1 , t -Bu L2 ) with CuX (X = Cl, Br, I) and CuX 2 . The outcome of the reaction of L1 with CuI depends on the metal-to-ligand ratio. Treatment of CuI with L1 in a 2 : 1 ratio affords the luminescent 2D CP Cu 4 I 4 (μ- L1 ) 2 n (CP1), whose grid-shaped network is built upon Cu 4 (μ 3 -I) 4 cubane-like clusters as secondary building units (SBUs), interconnected via bridging L1 ligands. The use of a 1 : 1 ratio gives a material, whose particularity is the coexistence of two topological isomers within the unit cell. The first one, {Cu(μ 2 -I) 2 Cu}(μ- L1 ) 2 n (CP2), consists of 1D ribbons. The second isomer having a 0D topology, {Cu(μ 2 -I) 2 Cu}(μ- L1 ) 2 D1, is built upon discrete molecular complexes, whose dinuclear Cu(μ 2 -I) 2 Cu rhomboid-shaped core is spanned by two bridging L1 ligands. Mixing CuBr with L1 in MeCN solution leads to an isostructural material incorporating both 0D {Cu(μ 2 -Br) 2 Cu}(μ- L1 ) 2 complex D2 along with the 1D isomer {Cu(μ 2 -Br) 2 Cu}(μ- L1 ) 2 n (CP3). However, only the 1D CP {Cu(μ 2 -Cl) 2 Cu}(μ- L1 ) 2 n (CP4) results from complexation of L1 with CuCl. A stoichiometry-dependence is also noticed upon treatment of CuI with L2 . Conducting the reaction in a 2 : 1 ratio yields the luminescent 2D CP Cu 4 I 4 (μ- L2 ) 2 n (CP5), whereas mixing equimolar amounts of the reactants produces 2D CP {Cu(μ 2 -I) 2 Cu}(μ- L2 ) 2 n (CP6). Structurally similar 2D CPs {Cu(μ 2 -X) 2 Cu}(μ- L2 ) 2 n (CP8 and CP9) result from complexation of L2 on CuBr or CuCl, respectively. Treatment of L2 with an excess of CuBr or CuBr 2 in refluxing acetonitrile led to the transfer of Br to the acetylenic triple bond, generating an olefinic halogenated dithioether ligand Bu L3 that coordinates to CuBr to generate a 1D network {Cu(μ 2 -Br) 2 Cu}(CH 3 CN)(μ- L3 ) n (CP9). Using different conditions (propionitrile at 293 K), the reaction of L2 and excess CuBr led to the formation of a 2D network {Cu(μ 2 -Br) 2 Cu}(μ- L2 )(μ- L3 ) n (CP10) incorporating both L2 and L3 in an alternating manner as assembling ligands. An isostructural chloro-analogue 2D {Cu(μ 2 -Cl) 2 Cu}(μ- L2 )(μ- L4 ) n (CP11) was obtained using CuCl or CuCl 2 . The crystallographic work is completed by thermal analyses and investigation of the luminescence properties of CP1 and CP5 at 77 and 298 K.