reaction prohibits the formation of polymers even at high temperature and pressure conditions . Radical ring-opening polymerization is one established method to homopolymerize a particular type of cyclic monomers bearing α-olefins . Even though this strategy can mitigate this chain transfer side reaction by rapidly rearranging the reactive secondary carbon-centered radicals to relatively stable positions via ringopening reactions, it creates unsaturated carbon-carbon double bonds that require further modification for polymer stability. Except for the radical ring-opening polymerization, other strategies to homopolymerize linear α-olefins under radical conditions are unreported. Another long-standing problem is the difficulty in homopolymerizing α-substituted styrenic and acrylate monomers when the substituent is larger than methyl. The well-accepted reason is the steric hindrance of α-substituent. Besides these two challenges associated with reactivity and steric congestion of the propagating radicals, sequence control is a longterm goal in radical polymerization as the polymer sequence is a crucial structure factor for material properties. In terms of sequence control, many efforts have been made to synthesize AB alternating sequences , ABA sequences , and AAB sequences based on different strategies . Sequenceregulated polymers with more than three units achieved by radical polymerization remain exclusive (Fig. ).