Self-assembly between Pt(phen)(edt) (phen=phenanthroline, edt=1,2-ethanedithiolate) and Cu(PPh3)2(MeCN)2(ClO4) (PPh3=triphenylphosphine) gave rise to formation of heterohexanuclear complex Pt4Cu2(edt)4(PPh3)6(ClO4)2(4H2O) (1). The complex was characterized by elemental analyses, ES-MS, UV-Vis, IR, 31P NMR spectroscopy and X-ray crystallography. The molecule consists of two Pt2Cu(edt)2(PPh3)3 units which has a centrosymmmetric inversion to give a cyclic heterohexanuclear skeleton. The PtⅡ and CuⅠ center adopt square-planar and trigonal coordination modes, respectively. The compound shows intense emission at 632 nm in the solid state and at 678 nm in frozen dichloromethane glass at 77 K.