Polyethylene-based polymers are the most widely used materials in the world, and their distinctive functions can be gained from the incorporation of various polar groups into the non-polar backbones that modifies the surface properties (e.g., adhesiveness, compatibility, toughness, adhesion, surface properties, etc.) of polyethylene. Copolymerization of ethylene with polar vinyl monomers provides a straightforward route to prepare functionalized polyethylene-based polymers. However, the current methods can only produce random copolymers, and is impossible for the synthesis of sequence-defined copolymers (Fig. ). For instance, free-radical polymerization can be applied in the production of ethylene/polar monomer (e.g., acrylates, acrylic acid, vinyl acetate) copolymers, this method encounters the substantial difference of reactivity ratios between ethylene and polar vinyl monomers and leads to random polymers with low molecular weights and chains containing a significant amount of branches. Moreover, in coordination polymerization the polar groups act detrimentally to the transition-metal catalysts, primarily due to the poisoning of the catalysts. In this scenario, the innovation of advanced strategies to produce the polyolefins consisting of polar blocks in accurate sequence control is highly desirable. Designing new α-olefins by integration of polar moieties into non-polar olefins backbone transforms the original copolymerization of ethylene with polar vinyl monomers into homopolymerization, and may overcome the sequence control problem in radical polymerization. Nevertheless, the homopolymerization of α-olefins is generally impeded by significant chain transfer process, in which the formation of more stable allylic radicals via hydrogen atom transfer (HAT) presents a major barrier to the successful assembly of polymer chains. In 1990s, Sato et al. reported the radical polymerization of vinyl ethers via 1,5-HAT, aiming to generate the oxygen-containing polymers (Fig. ). However, the polymerization proceeded through different pathways, leading to the polymers consisting of two chain structures. Moreover, these seminal studies were not applied to the construction of carbon-chain polyolefins.