The concerted dissociative reduction of di-tert-butyl peroxide (DTBP), dicumyl peroxide (DCP), and di-n-butyl peroxide (DNBP) is evaluated by both heterogeneous and homogeneous electron transfer using electrochemical methods. Electrochemical and thermochemical determination of the O-O bond energies and the standard potentials of the alkoxyl radicals allow the standard potentials for dissociative reduction of the three peroxides in N,N-dimethylformamide and acetonitrile to be evaluated. These values allowed the kinetics of homogeneous ET reduction of DTBP and DCP by a variety of radical anion donors to be evaluated as a function of overall driving force. Comparison of the heterogeneous ET kinetics of DTBP and DNBP as a function of driving force for ET allowed the distance dependence on the reduction kinetics of the former to be estimated. Results indicate that the kinetics of ET to DTBP is some 0.8 order of magnitude slower in reactivity than DNBP because of a steric effect imposed by the bulky tert-butyl groups. Experimental activation parameters were measured for the homogeneous reduction of DTBP with five mediators, covering a range of 0.4 eV in driving force over the temperature range -30 to 50 OC in DMF. The temperature dependence of the kinetics leads to unusually low preexponential factors for this series. The low preexponential factor is interpreted in terms of a nonadiabatic effect resulting from weak electronic coupling between the reactant and product surfaces. Finally, the data are discussed in the context of recent advances of dissociative electron transfer reported by Saveant and by German and Kuznestov. In total the results suggest that these peroxides undergo a nonadiabatic dissociative electron transfer and represent the first reported class of compounds where this effect is reported.