The electron-transfer oxidation and subsequent cobalt-carbon bond cleavage of vitamin B-12 model complexes were investigated using cobaloximes, (DH)(2)Co-III(R)(L), where DH- = the anion of dimethylglyoxime, R = Me, Et, Ph, PhCH2, and PhCH(CH3), and L = a substituted pyridine, as coenzyme B-12 model complexes and [Fe(bpy)(3)](PF6)(3) or [Ru(bpy)(3)](PF6) (3) (bpy = 2,2'-bipyridine) as a one-electron oxidant. The rapid one-electron oxidation of (DH)(2)Co-III(Me)(py) (py = pyridine) with the oxidant gives the corresponding Co(IV) complexes, [(DH)(2)Co-IV(Me)(py)](+), which were well identified by the ESR spectra. The reorganization energy (lambda) for the electron-transfer oxidation of (DH)(2)Co(Me)(py) was determined from the ESR line broadening of [(DH)(2)Co(Me)(py)](+) caused by the electron exchange with (DH)(2)Co(Me)(py). The lambda value is applied to evaluate the rate constants of photoinduced electron transfer from (DH)(2)Co(Me)(py) to photosensitizers in light of the Marcus theory of electron transfer. The Co(IV)-C bond cleavage of [(DH)(2)Co(Me)(py)](+) is accelerated significantly by the reaction with a base. The overall activation energy for the second-order rate constants of Co(IV)-C bond cleavage of [(DH)(2)Co-IV(Me)(py)](+) in the presence of a base is decreased by charge-transfer complex formation with a base, which leads to a negative activation energy for the Co(IV)-C cleavage when either 2-methoxypyridine or 2,6-dimethoxypyridine is used as the base.