Cu9S5 nanocrystals were synthesized from unsymmetrical [(Hex)(Me)NC(S)NC(O)C6H3(NO2)(2)-3,5](2)Cu(II) and [(Et)(Bu)NC(S)NC(O)C6H4-4-NO2](2)Cu(II) complexes by colloidal thermolysis in the presence of surfactant oleylamine. The unsymmetrical copper complexes were synthesized by the reaction of copper(II) acetate with N-[hexyl(methyl)carbamothioy1]-3,5-dinitrobenzamide and N-[ethyl(butyl)carbamothioy1]-4-nitrobenzamide. The complexes were used as single-source precursors for the preparation of Cu9S5 nanocrsytals. The Cu9S5 nanocrystals were characterized by X-ray powder diffraction and transmission electron microscopy.