The assembling of organic and inorganic components with emissive properties into new hybrid materials can provide multifunctional smart luminescent coordination networks [1]. Cyclic triimidazole (triimidazo[1,2-a:1',2'-c:1'',2''-e][1,3,5]triazine, L1) and its derivatives with pyridinic functional groups are useful tectons for molecular design. These molecules actively contribute to intermolecular stacking, making them useful participants for syntheses of new materials with intriguing supramolecular architectures. Recently, the inherent photoluminescent properties of cyclic triimidazole (L1) have been demonstrated [2], and some copper(I) halide coordination networks with this ligand have been reported [3]. Motivated by these results, we have prepared new coordination compounds starting from copper(II) acetate dihydrate and three triimidazole L1-L3 derivatives in a CH3CN/CH3OH/dmf solvent mixture. They include: one mono- [Cu(L2)2(CH3COO)2], 1, andtwo dinuclear [Cu2(L1)2(CH3COO)4], 2 and [Cu2(L3)2(CH3COO)4], 3 complexes. Compounds 1 and 3 crystallize in the triclinic space group P-1, and compound 2 crystallizes in the monoclinic space group P21/c. All compounds are centrosymmetric. The Cu(II) atom in centrosymmetric complex 1 has the N2O4 square-bipyramidal coordination core provided by two L2 ligands that coordinate in a monodentate mode, and bidentate chelate CH3COO- anions. The centrosymmetric dinuclear complexes 2 and 3 include paddle-wheel acetate dimer due to bridging function of four acetate anions, and capped by L1 or L3 in axial positions being mono-coordinated via imidazole nitrogen, Cu-N distances equal 2.217 and 2.238Å, respectively. The presence of stacking motifs in the reported coordination compounds responsible for the emission of free ligands [2] is a promising event for the ongoing research. Figure. Fragment of crystal packing in 2