A new complex {[Cu(hmtade)][Ni(dmit)2]}2·4DMSO(1)(hmtade=5,7,7,12,14,14-hexamethyl- 1,4,8,11-tetraazacyclotetradeca-4,11-diene, dmit=4,5-dimercapto-1,3-dithiole-2-thione, DMSO=dimethyl sulfoxide) was synthesized and characterized by means of elemental analysis, Infrared, Ultraviolet-visible spectroscopy, and X-ray structure analysis. Complex 1 belongs to monoclinic system, space group P21/n with a=1.49952(6) nm, b=1.77229(7) nm, c=3.1275(1) nm, β=102.442(1)°, V=8.1163(5) nm3, Dc=1.558 Mg/m3, Z=8, F(000)=3944, μ(Mo Kα)=1.637 mm-1, S=1.016, (Δ/σ)max=0.001, and final R1=0.0673, wR2=0.1672[I>2σ(I)]. Two independent structural units of [Cu(hmtade)][Ni(dmit)2] are found in an asymmetric unit along with four DMSO solvent molecules. Sulfur-bridged heterometal Cu—Ni complex is formed by one dmit ligand of [Cu(hmtade)][Ni(dmit)2]. The copper(Ⅱ) ion is a five coordinated square pyramidal environment, with Cu—N distances in the region of 0.1949(5)—0.2007(4) nm and Cu—S distances of 0.28913(18)—0.28952(18) nm. The nickel(Ⅱ) ion which is coordinated by four sulfur atoms of two dmit ligands is in the distorted square geometry, and the Ni—S distances fall in the range of 0.21729(16)—0.21905(17) nm. The N—H…O hydrogen bonds are formed between the nitrogen atom of hmtade ligand and DMSO solvent molecule, and the dimmer is formed through intramolecular S…S and S…H short contacts. Finally, one-dimensional zigzag chain, two-dimensional and three-dimensional networks are formed via S…S, S…C or C…H short contacts.