A d(8)-d(8) complex [Pt-2(mu-P2O5(BF2)(4)](4-) (abbreviated Pt(pop-BF2)(4-)) undergoes two le reductions at E-1/2 = -1.68 and E-P = -2.46 V (vs Fc(+)/Fc) producing reduced Pt(pop-BF2)(5-) and superreduced Pt(pop-BF2)(6-) species, respectively. The EPR spectrum of Pt(pop-BF2)(5-) and UV-vis spectra of both the reduced and the superreduced complexes, together with TD-DFT calculations, reveal successive filling of the 6p sigma orbital accompanied by gradual strengthening of Pt-Pt bonding interactions and, because of 6p sigma delocalization, of Pt-P bonds in the course of the two reductions. Mayer-Millikan Pt-Pt bond orders of 0.173, 0.268, and 0.340 were calculated for the parent, reduced, and superreduced complexes, respectively. The second (5-/6-) reduction is accompanied by a structural distortion that is experimentally manifested by electrochemical irreversibility. Both reduction steps proceed without changing either d(8) Pt electronic configuration, making the superreduced Pt(pop-BF2)(6-) a very rare 6p(2) sigma-bonded binuclear complex. However, the Pt-Pt sigma bonding interaction is limited by the relatively long bridging-ligand-imposed Pt-Pt distance accompanied by repulsive electronic congestion. Pt(pop-BF2)(4-) is predicted to be a very strong photooxidant (potentials of +1.57 and +0.86 V are estimated for the singlet and triplet d sigma*p sigma excited states, respectively).