Two previously reported compounds [Mo-2](CH3O)(2)M(CH3O)(2)[Mo-2] (Cotton, F. A.; Liu, C. Y.; Murillo, C. A.; Wang, X. Inorg. Chem. 2003, 42, 4619), in which [Mo-2] is an abbreviation for the quadruply bonded Mo-2(4+) unit embraced by three (p-anisyl)NC(H)N(p-anisyl) anions and M = Zn (1) or Co (2), have been chemically oxidized. One-electron oxidation products [Mo-2](CH3O)(2)M(CH3O)(2)[Mo-2](PF6) (3, M = Zn; 4, M = Co) and the two-electron oxidation product [Mo-2](CH3O)(2)Zn(CH3O)(OH)[Mo-2](PF6)(2) (5) have been isolated and structurally characterized. As expected, oxidations occur at the dimolybdenum units. The mono-charged cations in 3 and 4 have asymmetric molecular structures with two distinct [Mo-2] units. In each case, one of the [Mo-2] units has a lengthened Mo-Mo bond distance of 2.151 [1] Angstrom, as expected for one-electron oxidation, whereas the other remains unchanged at 2.115[1] Angstrom. These correspond to bond orders of 3.5 (sigma(2)pi(4)delta(1)) and 4.0 (sigma(2)pi(4)delta(2)), respectively. The crystallographic results thus show unambiguously that in the crystalline state, the mixed-valence compounds (3 and 4) are electronically localized and the unpaired electron is trapped on one [Mo-2] unit. These results are supported by the EPR spectra. The doubly oxidized compound 5 has two equivalent [Mo-2] units, both with a Mo-Mo bond distance of 2.149[1] Angstrom. EPR and magnetic susceptibility measurements for 5 indicate that there is no significant ferromagnetic or antiferromagnetic spin coupling and the species is valence-trapped.