The molecular structure and the binding energy of Pt(PR3)(2)(AlCl3) (R = H, Me, Ph, or Cy) were investigated by DFT, MP2 to MP4(SDTQ), and CCSD(T) methods. The optimized structure of Pt(PCy3)(2)(AlCl3) (Cy = cyclohexyl) by the DFT method with M06-2X and LC-BLYP functionals agrees well with the experimental one. The MP4(SDTQ) and CCSD(T) methods present similar binding energies (BE) of Pt(PH3)(2)(AlCl3), indicating that these methods provide reliable BE value. The DFT(M06-2X)-calculated BE value is close to the MP4(SDTQ) and CCSD(T)-calculated values, while the other functionals present BE values considerably different from the MP4(SDTQ) and CCSD(T)-calculated values. All computational methods employed here indicate that the BE values of Pt(PMe3)(2)(AlCl3) and Pt(PPh3)(2)(AlCl3) are considerably larger than those of the ethylene analogues. The coordinate bond of AlCl3 with Pt(PR3)(2) is characterized to be the sigma charge transfer (CT) from Pt to AlCl3. This complex has a T-shaped structure unlike the well-known Y-shaped structure of Pt(PMe3)(2)(C2H4), although both are three-coordinate Pt(0) complex. This T-shaped structure results from important participation of the Pt d(sigma) orbital in the sigma-CT; because the Pt d(sigma) orbital energy becomes lower as the P-Pt-P angle decreases, the T-shaped structure is more favorable for the sigma-CT than is the Y-shaped structure. [Co(alcn)(2)(AlCl3)](-) (alcn = acetylacetoneiminate) is theoretically predicted here as a good candidate for the metal complex, which has an unsupported M-Al bond because its binding energy is calculated to be much larger than that of Pt(PCy3)(2)(AlCl3).