Au₂₅L₁₈ (L = S(CH₂)₂Ph) clusters were prepared and characterized. The resulting monodisperse clusters were reacted with bis(pentafluorobenzoyl) peroxide in dichloromethane to form Au₂₅L₁₈⁺ quantitatively. The kinetics and thermodynamics of the corresponding electron transfer (ET) reactions were characterized via electrochemistry and thermochemical calculations. Au₂₅L₁₈⁺ was used in homogeneous redox catalysis experiments with a series of sym-substituted benzoyl peroxides, including the above peroxide, bis(para-cyanobenzoyl) peroxide, dibenzoyl peroxide, and bis(para-methoxybenzoyl) peroxide. Peroxide dissociative ET was catalyzed using both the Au₂₅L₁₈/Au₂₅L₁₈⁻ and the Au₂₅L₁₈⁺/Au₂₅L₁₈ redox couples as redox mediators. Simulation of the CV curves led to determination of the ET rate constant (k_ET) values for concerted dissociative ET to the peroxides. The ET free energy ΔG° could be estimated for all donor–acceptor combinations, leading to observation of a nice activation–driving force (log k_ETvs. ΔG°) relationship. Comparison with the k_ET obtained using a ferrocene-type donor with a formal potential similar to that of Au₂₅L₁₈/Au₂₅L₁₈⁻ showed that the presence of the capping monolayer affects the ET rate rather significantly, which is attributed to the intrinsic nonadiabaticity of peroxide acceptors.