Reduction of 2-(BMes(2))pyrene (B-1) and 2,7-bis(BMes(2))pyrene (B-2) gives rise to anions with extensive delocalization over the pyrenylene bridge and between the boron centers at the 2- and 2,7-positions, the typically unconjugated sites in the pyrene framework. One-electron reduction of B-2 gives a radical anion with a centrosymmetric semiquinoidal structure, while two-electron reduction produces a quinoidal singlet dianion with biradicaloid character and a relatively large S-0-T-1 gap. These results have been confirmed by cyclic voltammetry, X-ray crystallography, DFT/CASSCF calculations, NMR, EPR, and UV-vis-NIR spectroscopy.