The dinudear NNP-ligand copper(I) complex [o-N=CH(C4H3N)-PPh2C6H4](2)C(u)2 (1) has been synthesized by the reaction of (CuMes)(4) (Mes = 2,4,6-Me3C6H2) with N-((1H-pyrrol-2-yl)-methylene)-2-(diphenylphosphino)benzenamine under an elimination of MesH. Further reaction of 1 with an excess of S-8 produced a mononuclear Cu(II) complex [o-N=CH(C4H3N)-P(S)Ph2C6H4](2)Cu (5) and CuS. CuS was identified by Raman spectroscopy and 1 and 5 were clearly confirmed by X-ray crystallography. The N-heterocyclic carbene was employed to react with 1 to give a mononuclear [o-N=CH(C4H3N)-PPh2C6H4]Cu{C[N(iPr)CMe](2)} (2). The reactions of 2 were carried out with 1/8, 2/8, and 5/8 equiv of S-8, leading to compounds [o-N=CH(C4H3N)-P(S)Ph2C6H4]Cu{C[N(iPr)CMe](2)} (3), [o-N=CH(C4H3N)-P(S)Ph2C6H4]Cu (4), and 5 respectively, in which CuS was generated in the third reaction and S=C[N(iPr)CMe](2) in the latter two reactions. The clean confirmation of 2-4 demonstrates a stepwise reaction process of 1 with S-8 to 5 and CuS and the N-heterocyclic carbene acts well as a trapping agent.