Self-assembly cluster compound [WS4Cu3(PPh2Py)3Br]2·CH3OH (1) was synthesized by the reaction of (NH4)2WS4,CuBr and diphenyl-2-pyridyl-phosphine (PPh2Py) in CH3OH solution under a purified nitrogen atmosphere using standard Schlenk techniques.Its structure was determined by X-ray crystallography.It crystallizes in the triclinic crystal system P-1 space group with α=1.178 6(1)nm,b=1.302 6(1)nm,c=1.9917(2)nm,α=74.671(7)°,β=86.188(8)°,γ=64.141(6)°,V=2.649 5(5)nm',Z=1.The W center is slightly distorted from tetrahedral coordination geometry,and the structure is built up from three [Cu(PPh2Py)]+ units bridged by WS2-4 multifunctional ligand to form a tetranuclear symmetrical cube-like molecule.Measurement of the nonlinear optical (NLO) properties using the Z-scan technique with an 8 ns pulsed laser at 532 nm shows that the compound possesses NLO absorption and effective self-focusing effect at α2=6.7×10-11m/W and n2=5.64×10-18m2/W in a 1.5×10-4mol/L DMF solution.