The starting complex [PtCl{(κ2-P,C)P(OC6H4) (OPh)2}SMe2], 3, was prepared by a new method using the reaction of [PtCl2(P(OPh)3)2] with 1 equiv of PtCl2 in xylene under reflux condition followed by treatment with an excess amount of SMe2. Reaction of [PtCl{(κ2-P,C)P(OC6H4) (OPh)2}SMe2], 3, with 0.5 equiv of dppf (1,1′-bis(diphenylphosphino)ferrocene), dppm (bis(diphenylphosphinomethane)) ligands and 1 equiv of dppe ligand, PˆP, gave the dinuclear complexes [Pt2Cl2{(κ2-P,C)P(OC6H4) (OPh)2}2(μ-dppf)], 4a, [Pt2Cl2{(κ2-P,C)P(OC6H4) (OPh)2}2(μ-dppm)], 4b, and mononuclear bis-chelated [Pt{(κ2-P,C)P(OC6H4) (OPh)2}2(dppe)]Cl, 5, respectively. The complexes were fully characterized using multinuclear (1H and 31P) NMR spectroscopy and elemental analysis. The structure of typical complex 4a was further determined by X-ray crystallography. The optimized structures of the complexes in their dichloromethane solutions were obtained from DFT calculations. These optimized structures were used to determine the frontier molecular orbitals of the complexes and also the nature of their electronic transitions.