The anion radical of mono-bromo-[8]annulene was generated in the absence of ion association, and the EPR-measured spin densities can be explained in terms of the odd electron occupying MOs: Psi(4)' [2root(n(2) + 1)](-1)(Psi(1) + nPsi(2) - Psi(3) - nPsi(4) + Psi(5) + nPsi(6) - Psi7 - nPsi(8)) and Psi(5)' = [2root(n(2) + 1)](-1)(Psi(1) - nPsi(2) Psi(3) + nPsi(4) + Psi(5) - nPsi(6) - Psi(7) + nPsi(8)) where n > 1. This anion radical subsequently disproportionates to its corresponding dianion and neutral molecule. The dianion then undergoes a loss of Br-, leaving the [8]annulenyl carbanion, which can abstract a proton from either HMPA or liquid ammonia. The pseudo-ortho-bromo-[8]annulenyl carbanion also loses Br- to give [8]annulyne, which can be stabilized in the form of its anion radical. The g value of the anion radical of [8]annulyne indicates that the extra strain energy due to the presence of the triple bond causes the two highest occupied MOs (degenerate in the anion radical of [8]annulene) to be slightly split.