We conceive to develop an efficient method for radical polymerization of α-olefins and construct sequence-defined polyethylene-based polymers with diverse polar blocks. In the hypothesis (Fig. ), strategically designed hexene derivatives substituted with two electron-deficient groups are employed as monomers. Mechanistically, the in-situ generated secondary alkyl radical abstracts H-atom from remote site, mainly via 1,5-HAT, to form a new tertiary alkyl radical species (b) that engages in the chain propagation. The driving force for the HAT has two folds: the tendency of H-abstraction from electron-deficient carbon by nucleophilic alkyl radical and the formation of a more stable tertiary alkyl radical. As a result, the fast intramolecular HAT suppresses the intermolecular chain transfer and facilitates the desirable polymerization of α-olefins. Alternatively, if the C-H bond is absent, the group transfer takes place instead of HAT to induce the polymerization.