The reaction between [PtCl2(L-L)] (L-L = dppe, dppp, dppb, dppf, Phen and Bipy) or [PtCl2(PPh3)2] with 1-benzyl-3-phenylthiourea (H2BPT) in a basic medium (CHCl3/EtOH) created new coordinated square planner Pt(II) complexes with [Pt(BPT)(L-L)] (1–4,6,7) and [Pt(BPT)(PPh3)2] (5) types. These complexes were fully characterized by analytical and spectroscopic techniques (i.e., IR, UV. Vis., 1H, and 31P NMR). The results indicated that the thiourea derivative ligand act as a dianion ligand bonded through both S and N atoms in a chelating mode or as a mono-anion ligand coordinated through a sulfur atom with Pt(II) ion. Cytotoxicity activity was performed by the MTT assay to determine anti-cancer activities against MCF-7 breast cancer cells. The study indicated that IC50 values for MCF-7 cells were 10.96–78.90 µM. Additionally, the complexes [Pt(BPT)(dppe)] (1), [Pt(BPT)(PPh3)2] (5), and [Pt(BPT)2(Bipy)] (7) were investigated theoretically, where their quantum parameters were evaluated using the Gaussian 09 program using the theory of B3LYP/Def2TZVP//B3LYP/Lanl2dz. The calculation results confirmed the optimized structures of the complexes square planar geometry. However, the calculated bond lengths and angles showed a slightly distorted square planar geometry due to the trans influence of the sulfur atom. Additionally, complexes of [Pt(BPT)(dppe)] (1) and [Pt(BPT)(PPh3)2] (5) showed higher stability compared to [Pt(BPT)2(Bipy)] (7), which can be attributed to the higher back-donation of (1) and (5) complexes. Furthermore, among the three complexes, the [Pt(BPT)2(Bipy)] (7) complex possessed the lowest HOMO–LUMO gap, which may be a good candidate as the photo-catalyst material.