A complex, Ni (en)2 Ag3 (CN) 5 (en = ethylenediamine), was obtained through the reaction of [Ag (CN) 2] -units with Ni Ⅱ -diamine cation [Ni (en)2] 2 +, and the structure was determined by single crystal X-ray diffraction. It is indicated that the complex has a 3D architecture through the silver-silver interactions and the bridging cyano groups. This complex displays interesting luminescent properties caused by argentophilicity at room temperature in solid state.