A series of binuclear copper chelate with α-diimine ligand have been synthesized both in Cu(I) and Cu(II) form. Metatheses between lithium tetracyanoquinodimethane, LiTCNQ, and the binuclear copper chelate yielded semiconductive complexes in the form of Cu2L(TCNQ)2, Cu2L(TCNQ)2I2, Cu2L2)TCNQ)I, and Cu2L2(TCNQ)2I2 where L is binucleating α-diimine ligand. All the complexes have been characterized by elemental analysis, infrared, electronic, mass, electron spin resonance spectra, magnetic susceptibility and electrical conductivity measurements. The conductivities were in the range of 10−3 to 10−5Scm−1 with activation energy of 0.17 eV. The electron spin resonance spectra show the results of strong coupling between copper and TCNQ. The coupling strength decreased as the temperature decreasing from 300°K to 77°K. The compounnds can be formulated as [Cu2LL][TCNQ−]I, and [CuII2L2][TCNQ−]2I2; a partial electron transfer occurs from CuI to TCNQ− in n-type semiconductor form or TCNQ− to CuII in p-type semiconductor form.