The reactions of K{S(O)COR} (R=iPr, iBu) with Cu(CH3CN)4PF6 / Au(THT)Cl and PPh3/dppf in stoichiometric ratios afford the compounds Cu{S(O)COiPr}(PPh3)2 (1), Au{S(O)COiPr}(PPh3)2 (2), [Cu4{S(O)COiBu}3(PPh3)6]+ (3), Au{S(O)COiBu}(PPh3)2 (4) and Cu{S(O)COiPr}(dppf) (5) quantitatively. The complexes are characterized by the combination of elemental analysis, IR, 1H, 31P NMR, mass spectrometry (1, 2), cyclic voltammetry (5) and single crystal X-ray techniques. In all of the monomeric complexes, CuI and AuI possess tricoordinate trigonal planar geometry but in 3, three copper atoms adopt tetrahedral coordination geometry and the fourth copper atom is trigonally coordinated. A mono-dentate binding mode through sulfur atom [ROC(O)S−] is observed for the ligands in all the mononuclear complexes. Interestingly in 3 a bridging mode (κ3: μ2-S, μ-O) has been observed for the first time in monothiocarbonate chemistry. Complexes 2 and 4 show prominent luminescent behavior emitting bluish green at 472 and 467nm, respectively, in solid state at 77K. In fact these are the first examples of any monothiocarbonate complexes exhibiting photoluminescent behavior. Further an unexpected gold sulfide complex Au4S2(PMe3)4 (6) formed probably via the CS bond scission of monothiocarbonate ligand has also been reported.