A new 2-tosylaminobenzylidene-2′-amino-5′-chlorothiophenol ligand and its mono- and binuclear copper complexes are synthesized. Their structures are characterized by IR, 1H NMR, and magnetochemistry. In the copper binuclear complex there is the antiferromagnetic exchange interaction between paramagnetic centers. The dimeric structure of the copper complex is confirmed by X-ray absorption spectroscopy. The addition of pyridine to the dimeric cooper complex results in the formation of a paramagnetic monomeric structure in which pyridine is coordinated to metal via the nitrogen atom.