This article presents a combined experimental and computational study of a new oxorhenium(V) complex of thiazolidine-2,4-dione (HTDO). The complex has been synthesized by direct reaction of NH4ReO4 with thiazolidine-2,4-dione in the presence of Na2S2O6 as a reducing agent. The complex [ReO(TDO)(H2O)3](S2O8) has been characterized by spectroscopy (FT-IR, NMR, UV-vis, mass), thermogravimetry, microanalysis, and HPL chromatography.