Treatment of bis(diphenylphosphino)methane(dppm)and 2-(diphenylphosphanyl)pyridine(dpppy)with Cu(CH3CN)4BF4 afforded a dinuclear Cu(I)complex[Cu2(dpppy)2(dppm)(CH3CN)](BF4)2?3CH2Cl2(1).Complex 1 was structurally characterized by X-ray single-crystal analysis and its photophysical properties were studied in detail.It crystallizes in triclinic space group Pī with a = 13.0834(8),b = 13.5568(8),c = 21.8544(11)?,a = 76.090(5)°,β = 80.803(5)°,y = 64.582(6)°,V = 3391.3(3)?3,Z=2,Mr= 1507.42,Dc = 1.476 g/cm3,F(000)=1532,GOOF= 1.071,the final R = 0.0700 for 9041 observed reflections with I＞ 2a(I)and wR = 0.2063 for all data.The complex contains a Cu2-core structure surrounded by one dppm and two dpppy ligands in a head-to-head arrangement.In the crystalline phase,complex 1 exhibits bright bluish-green photoluminescence(λmax = 488 nm)with high quantum yield(? = 0.57)at room temperature.It is still a relatively high emission quantum yield(? =0.36)in doped PMMA thin film with 20 wt％dopant of complex 1.The emission peaks of 1 in dichloromethane solution and doped PMMA(20 wt％)thin films are 510 and 494 nm,respectively,showing a very slight bathochromic shift compared to that in crystalline phase.This phenomenon might be attributed to its rigid conformation that precludes the possible distortion of copper centers in the excited state.