The possible mechanisms of decomposition of benzoyl peroxide were investigated by the method of density functional theory with the exchange-correlation functionality of B3LYP, a basis set of 6-31G (d, p). It was carried out a comparative analysis of the quantum chemical calculations of the electronic structure of carbon nanoclusters simulating the active surface of sp < sub>2 carbon materials, including their modifications by the heteroatoms N and O. The energy parameters of the benzoyl peroxide molecule and all possible products of its decomposition, as well as the interaction of the free radical Ph-COO• with model graphite-like nanoclusters were considered. The calculations are compared with the experimental results of the catalytic activity of the varieties of activated charcoal and the catalase enzyme in the reaction of the benzoyl peroxide decomposition in a non-aqueous medium. It has been established that in the benzoyl peroxide molecule, regardless of the polarity of the medium, the weakest is the bond (O-O). The greatest ability to decompose benzoyl peroxide, which is much larger than that of catalase, was detected on the N-containing carbonaceous materials. It is shown that the free radical Ph-COO• is lighter and kinetically, and thermodynamically interacted with the graphite-like plane of the model N-containing carbon nanoclusters.