We have devised a strategy of switchable remote hydrogen atom or group transfer, which is applicable for the production of polyethylene-based polymers consisting of various polar blocks. A variety of new α-olefin monomers are designed for the radical polymerization. This innovative technique facilitates the construction of a diverse array of AAB or ABC sequence-defined carbon-chain polyolefins. All these sequencedefined polyethylene-based polymers are difficult to prepare by current methods. These research endeavors pave a new avenue for the precise synthesis functionalized polyolefins, potentially opening the prospects of the fabrication of high-performance materials.