A novel strategy for the synthesis of main-chain polymers through radical ring-closing/ring-opening cascade polymerization is reported. Efficient radical cyclopolymerization was achieved through systematic optimization of the electronic properties of 1,6-diene structures. Fusing 1,6-diene with allylic sulfide or allylic sulfone motifs enabled a ring-closing/ring-opening cascade reaction that provides a strong driving force for the ring-opening polymerization of large macrocyclic monomers. The ability of 1,6-diene-fused allylic sulfone to undergo efficient SO2 extrusion generated a propagating alkyl radical capable of reversible deactivation. This strategy provides a general platform for the synthesis of polymers incorporating complex main-chain structures and degradable functionalities.