The mononuclear nickel complex [Me2CHN(PPh2)(2)]Ni(SCH2Ph)(2) has been synthesized by the reaction of [Me2CHN(PPh2)(2)]NiCl2 with PhCH2SH and Et3N in CH2Cl2 in 77% yield. The title complex was structurally characterized by H-1 NMR, P-31{H-1} NMR spectroscopy as well as X-ray crystallography. The X-ray diffraction analysis reveals that the molecular structure consists of a central nickel atom coordinated by two phosphorus atoms of the bis(diphenylphosphanyl)amine and two sulfur atoms of benzylthiolate. There are no classical hydrogen bonds but van der Waals' interactions exist to stabilize the solid state in the crystal packing.