This article summarizes and presents the obtainable characteristic IR spectra of the existing heterothiometallic cluster compounds containing the [MXS 3 ] 2− (X=O, S; M=V, Mo, W, Re) moiety. The MS stretching vibration modes are classified into four categories including ν(MS t ), ν(Mμ 2 -S), ν(Mμ 3 -S) and ν(Mμ 4 -S) according to the different conjunction ways between the transition metal and sulfur atoms. The structures of the heterothiometallic cluster compounds could be inferred from their characteristic IR spectra, the core structure's symmetry of the heterothiometallic clusters and the M/M′ ratio.