In this article, three types of metal ions with different oxidation state as mercury(Ⅱ), cerium(Ⅲ) thorium(Ⅳ) have been reacted with captopril drug (CAP). The isolated solid complexes were explained using elemental analysis, conductance measurements, infrared and ¹H-NMR spectroscopy as well as the thermo gravimetric (TG/DTG) analysis. The micro analytical and spectroscopic results for all CAP complexes were agreement with the speculated structures. The stoichiometry for divalent Hg² , trivalent Ce³ and tetravalent Th⁴ metal ions with CAP ligand was established with 1:2 (Mⁿ :CAP) molar ratio. The qualitative analysis showed that in case of the mercury(Ⅱ) complex, the chloride ions didn’t involved in the complexity, suggesting formula [Hg(CAP)₂] in neutral form. However, regarding both Ce(Ⅲ) and Th(Ⅳ) complexes as [Ce(CAP)₂(NO₃)]·3H₂O and [Th(CAP)₂(NO₃)₂(H₂O)]·3H₂O formulas, the nitrate group is existed inside the coordination sphere. The infrared analysis data proved that CAP drug act as a bidentate ligand with the metal ions of Ce(Ⅲ) and Th(Ⅳ) through oxygen carbonyl group C=O and oxygen of the deprotonated carboxylic COOH group, while for the Hg(Ⅱ) complex, the CAP acts as a bidentate ligand through oxygen of C=O group and sulfur atom of the deprotonated —SH group. Thorium(Ⅵ) complex has a nine-coordinate geometry, while Hg(Ⅱ) and Ce(Ⅲ) have a four and six-coordination behaviors respectively. The ¹H-NMR data of the CAP compound has a singlet sharp signal at 1.90 ppm due to the proton of —SH group, this peak absent in the spectrum of the Hg(Ⅱ) CAP complex upon the deprotonated of thiol group.