Trinuclear metal clusters of Co, Mn, and Co/Mn hybrid of [Mn3(O)(CH3COO)6-(py)3ClO4], [Co3(O)(CH3COO)6-(py)3- ClO4], [Co2Mn(O)(CH3COO)6-(py)3ClO4], and [CoMn2(O)(CH3COO)6-(py)3ClO4] were prepared and characterized by FT-IR and UV–Vis spectroscopic techniques. These homogeneous catalysts were investigated in the epoxidation of cyclohexene in the presence of H2O2/O2 under mechanical stirring conditions. The effect of the oxidant, reaction temperature, kind of promoter, and solvent system were investigated on conversion and epoxide selectivity. In these systems, NaBr was selected as a promoter of oxidation based on standard potential (X = Cl-, Br-) toward Co3?, and Mn3?. These homogeneous catalytic systems can be the perfect choice for epoxidation of cyclohexene with good conversion and high epoxide selectivity over short periods.