The reaction of [NBu₄][(C₆F₅)₂Pt(μ-PPh₂)₂Pt(μ-PPh₂)₂Pt(O,O-acac)] (48 VEC) with [HPPh₃][ClO₄] gives the 46 VEC unsaturated [(C₆F₅)₂Pt¹(μ-PPh₂)₂Pt²(μ-PPh₂)₂Pt³(PPh₃)](Pt²-Pt³) (1), a trinuclear compound endowed with a Pt-Pt bond. This compound displays amphiphilic behavior and reacts easily with nucleophiles L, yielding the saturated complexes [(C₆F₅)₂Pt^II(μ-PPh₂)₂Pt^II(μ-PPh₂)₂Pt^II(PPh₃)L] [L = PPh₃ (2), py (3)]. The reaction with the electrophile [Ag(OClO₃)PPh₃] affords the adduct 1·AgPPh₃, which evolves, even at low temperature, to a mixture in which [(C₆F₅)₂Pt^III(μ-PPh₂)₂Pt^III(μ-PPh₂)₂Pt^II(PPh₃)₂]²⁺(Pt^III-Pt^III) and 2 (plus silver metal) are present. The nucleophilic nature of 1 is also demonstrated through its reaction with cis-[Pt(C₆F₅)₂(THF)₂], which results in the formation of [Pt₄(μ-PPh₂)₄(C₆F₅)₄(PPh₃)] (4). The structure and NMR features indicate that 1 can be better considered as a Pt^II-Pt^III-Pt^I complex instead of a Pt^II-Pt^II-Pt^II derivative. Theoretical calculations (density functional theory) on similar model compounds are in agreement with the assigned oxidation states of the metal centers. The strong intermetallic interactions resulting in a Pt²-Pt³ metal-metal bond and the respective bonding mechanism were verified by employing a multitude of computational techniques (natural bond order analysis, the Laplacian of the electron density, and localized orbital locator profiles).