In conclusion, we have disclosed an innovative GTRP method, which facilitates the formation of high molecular-weight polymers endowed with excellent precision in terms of composition-spanning both homopolymers and copolymers-as well as intricate macromolecular structures. This versatile technique enables the generation of linear α-olefin polymers through a radical homopolymerization process. Moreover, by adjusting the monomer polarity, we have achieved the synthesis of sequence-defined PAN-type copolymers. This method features the production of a broad diversity of polymers, the easy availability of monomers, and the industrialization potential. Our research endeavors continue to explore and utilize the GTRP strategy for crafting unprecedented polymer structures.