It is found that ferrocene in the presence of small amounts of pyrazine carboxylic acid (PCA) effectively catalyzes the oxidation of benzene to phenol with hydrogen peroxide. Two main differences upon the oxidation of two different substrates, i.e., cyclohexane and benzene, with the same H2O2-ferrocene-PCA catalytic system are revealed: the rates of benzene oxidation and hydrogen peroxide decomposition are several times lower than the rate of cyclohexane oxidation at close concentrations of both substrates, and the rate constant ratios for the reactions of oxidizing particles with benzene and acetonitrile are significantly lower than would be expected for reactions involving free hydroxyl radicals. The overall rate of hydrogen peroxide decomposition, including both the catalase and oxidase routes, is lower in the presence of benzene than in the presence of cyclohexane. It is suggested on the grounds of these data that a catalytically active particle different from the one generated in the absence of benzene is formed in the presence of benzene. This particle catalyzes hydrogen peroxide decomposition less efficiently than the initial complex and generates a dissimilar oxidizing particle that exhibits higher selectivity. It is shown that reactivity of the system at higher concentrations of benzene differs from that of an initial system not containing an aromatic component with the capability of π-coordination with metal ions.