With our methods, these sequence-controlled copolymers doped with sulfur atoms can be easily accessed (P7-P10). It is worth noting that in a conventional acrylonitrile-styrene copolymer backbone, two monomers are connected head-to-tail. Starting from different monomers, acrylonitrile and styrene are connected head-to-head and head-to-tail respectively in the poly (acrylonitrile-styrene-sulfur atom) (P9 and P10). As head-to-head vinyl polymers are extremely rare in radical chain polymerization, these new structures may open up new regime in the understanding of polymer structure-property relations. With a substitution at the allylic position, polymers with successive tertiary carbons can be synthesized (P10-P12). This cyano migration strategy also works with fluoro olefinic monomer (P13). It is widely accepted that α-substituted (except for methyl) styrenic and acylate monomers are challenging to homopolymerize due to the steric hindrance. In our case, the bulky propagating tertiary carbon radicals can translocate to sulfur atoms via cyano migration, enabling the addition to the next monomers (P15-P20). We also demonstrate the success of radical homopolymerization of cyclopropenyl monomers for the first time, resulting in polymers with cyclopropane moieties in the main chain. (-)-Isopulegol, an abundant natural substance used to access the monomer for the synthesis of P23. With thiocyanate substituted 1,3-diene monomer, binary copolymers with double bonds within the main chain can be obtained, providing possibilities for further polymer chain elaboration. It is accepted that 1,3-diene can be radically homopolymerized, so the polymerization did not occur completely via the cyano group migration pathway.