Abstract <p>The reactions of addition of allyl monomers (allyl chloride, allylbenzene, allyl acetate) vinyl-type growth radicals to fullerene C₆₀ at the radical polymerization in the presence of fullerene have been studied by the density functional theory method. Reactivity toward fullerene decreases in the series of vinyl-type growth radicals allylbenzene–allyl acetate–allyl chloride. The fullerenyl radicals are able to interact with monomer molecules to form growth radicals with fullerene in the main chain. This fact explains the increase in the percentage of allylic units in copolymers of allyl and vinyl monomers obtained at the radical copolymerization in the presence of fullerene C₆₀. However, such a reaction has an activation enthalpy exceeding that of the free-radical propagation reaction of allyl monomers by 2.8–3.7 times. In terms of concentration factor, such a reaction still occurs in polymerization systems, where the concentration of monomers is much greater than the concentration of growing and fullerenyl radicals. Moreover, the reactivity of allyl chloride, allyl acetate and allylbenzene toward fullerenyl radicals practically does not differ. The presence of fullerene in the main chain affects the reactivity of such allyl growth radicals, making them more reactive toward monomers in the case of allyl acetate and allylbenzene.</p>