Abstract：A new rhenium SNS/S mixed ligand complex [ReO(MPMEP)(BMPBA)][ReO (MPMEP)(BMPBA)] [MPMEP = 1-(2-methoxyphenyl)-(4-mercaptoethyl)- piperazine, BMPBA = N,N-bis(2-mercaptoethyl)-benzylamine] has been prepared. The single crystal structure of the complex was determined by X-ray diffraction method. It belongs to triclinic crystal system, space group P1 with a = 0.93604(19) nm, b = 1.1044(2) nm, c = 1.3823(3) nm; α = 89.19(3)°, β = 74.50(3)°, γ = 75.04(3)°; Z = 1, V = 1. 3281(5) nm~3, μ = 4.836 mm~(-1), F(000) = 677, R = 0.0403, wR = 0.0673. Both [ReO(MPMEP)(BMPBA)] of the complex adopt distorted trigonal bipyramidal geometry, with the basal plane defined by the SS atoms of the tridentate ligand and the oxo-group. The N of the tridentate ligand and the S of the monodentate ligand occupy two apical positions. Ionization of the sulphur atoms leads to a neutral compound.