A hexanuclear copper(Ⅰ) cluster [Cu6(C5H4NS)6] was synthesized by means of the hydrothermal reaction of [Cu(PPh3)2(MeCN)2]ClO4 with(2-mercaptopyridine-1-oxide) in the presence of 2-butanol,Et3N and water and characterized by elemental analysis,IR,TGA and solid state fluorescence spectroscopy as well as X-ray diffractometry.The crystallographic data for the title complex,C15H12Cu3N3S3,are Mr=521.08,monoclinic space group P2(1)/n and the cell parameters are: a=0.958 59(6) nm,b=(1.604 85(12) nm),(c=)0.122 712(10) nm,β=108.863(2)°,V=1.786 4(2) nm3,Z=4,Dc=(1.937 Mg/m3),R1=0.030 1,ωR2=0.031 5(I>2σ(I)),F(000)=1 032,μ=3.890 mm-1,R(int)=0.050 1,S=0.598.The title complex exhibits highly thermal stability and strong low energy fluorescence((λ=)744 nm) when it is irradiated by the light(λ=468 nm) in solid state at room temperature.