Radical copolymerization of butyl methacrylate with 2,3‐dimethylbutadiene in the presence of Al(C2H5)2Cl or ZnCl2 results in alternating copolymers. The nature of active centers and the mechanism of polymerization in these systems have been studied by means of ESR measurements in combination with calorimetry at low temperatures. The active centers are monoradicals propagating by alternative addition of single monomer molecules; thus the reaction can be described in terms of a conventional kinetic scheme of radical additional polymerization. Participation of binary donor—acceptor complexes of the monomers in the reaction has not been confirmed. Similar conclusions have been drawn for the other alternating system studied, maleic anhydride–2,3‐dimethylbutadiene. The feasibility of formation of alternating copolymers in the studied systems by the conventional mechanism of binary radical copolymerization has been confirmed by qualitative quantum‐chemical treatment of the propagation reactions with due account to the donor–acceptor interactions in the transition state.

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