Radical polymerization has emerged as a powerful technique for synthesizing polymeric materials that are prevalent in our everyday lives. This flexible and economically viable process has been extensively utilized to produce a wide variety of products, spanning from food packaging to textiles and fibers. One of the persistent challenges in radical polymerization is the inability of non-activated olefins to undergo radical homopolymerization, which is hindered by degradative chain transfer side reactions. This fact is well-documented in polymer chemistry and related textbooks. Despite this limitation, these olefins can copolymerize with sulfur dioxide (SO2), another non-homopolymerizable monomer, to produce poly(olefin sulfone)s. Poly(olefin sulfone)s are significant not only because they serve as a classic example of alternating radical copolymerization but also due to their widespread use, evidenced by numerous patents from the industry. However, the typical polymerization process involving the use of corrosive SO2, which requires low-temperature liquefaction within specialized glass or stainless steel pressure vessels, poses challenges due to its inherent hazards and practical limitations (Figure ). Radical rearrangements are advanced techniques for editing molecular structures, offering creative solutions to problems faced in radical polymerization. Recently, radical smiles rearrangements have been well developped for achieving aryl migrations, which enable structural changes. In these transformations, SO2 serves as a non-permanent linker that connects two functional groups, a strategy also employed in radical ring-opening polymerization by the Niu group. However, the spontaneous removal of SO2 during polymerization, driven by entropic factors, prevents the synthesis of poly(olefin sulfone)s. In contrast, the Wang group has recently introduced a new method for smiles rearrangements that retains SO2 within the molecular structures (Figure ). Our research group has been interested by the radical homopolymerization of functionalized αolefins. Inspired by Wang's seminal report, we envision that upon initiation, secondary carbon radicals are formed, subsequently trigging aryl migration to generate sulfonyl radicals. These electrondeficient sulfonyl radicals can then propagate the polymerization by adding to another α-olefin monomer. Through this radical relay mechanism, the radical homopolymerization of sulfonyl α-olefins can proceed with propagating sulfonyl radicals. Herein, we introduce a novel strategy for the radical homopolymerization of sulfonyl α-olefin monomers, yielding sequence-regulated poly(vinylbenzothiazole-olefin-sulfone)s for the first time. Notably, the production of ABC-sequenceregulated polymers remains relatively unexplored compared to the extensively studied AB alternating, ABA, and AAB sequences. This unique polymerization process relies on 1,4-aryl migrations under radical conditions. Moreover, this unprecedented strategy can be extended to radical homopolymerization involving 1,5-aryl migrations, furnishing polysulfones with an additional methine unit within the main chains. In contrast to conventional polysulfone synthesis methods employed in academia and industry, which primarily adjust properties by altering olefin monomers, this "SO2-free" approach offers a versatile means of tuning the chemical space by tailoring the sequence composition (Figure ). The sulfonyl monomers M1 can be readily obtained through the substitution of homo-allylic bromides with thiols, followed by oxidation (See SI for synthetic details). Initially, the radical homopolymerization of M1 was investigated using tert-butyl peroxybenzoate (TBPB) as an initiator in chlorobenzene (PhCl) at a concentration of 2 M and a temperature of 80 °C. After 24 hours, a light-yellow product precipitated from the reaction mixture. The polymeric products exhibited limited solubility in polar solvents such as N, N-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). Analysis by size exclusion chromatography (SEC) revealed a number-averaged molecular weight (Mn) of 19.8 k and a dispersity (Đ) of 5.91 (Table , entry 1). Subsequently, the effect of solvents on polymerization was examined. Acetone was found to yield the polysulfones with highest conversion (Table , entries 2-5). Additionally, 1,1'-Azobis(cyclohexane-1-carbonitrile) (V-40) could also initiate polymerization, albeit with a reduced conversion (Table , entry 6). When the polymerization was conducted in a more diluted solution, the conversion decreased to 24% (Table , entry 7). The limited solubility of the obtained polymers only permitted the acquisition of the 1 H nuclear magnetic resonance (NMR) spectrum, which hindered the determination of the main chain structures. However, we were pleased to observe that the solubility of the polymers could be significantly enhanced by using a monomer (M2) with a methyl group introduced on the vinyl position. The polymerization proceeded with an 62% conversion, giving polymers with a Mn of 31.1k and a dispersity of 2.13 (Table , entry 8). Since the sequence of the polymer main chain is unprecedented, the polymer chain structure (P2) was unambiguously characterized by 1 H & C nuclear magnetic resonance (NMR) spectroscopy, 1 H-1 H correlation spectroscopy (COSY), 1 H- C heteronuclear multiple bond correlation (HMBC), and 1 H- C heteronuclear single quantum coherence (HSQC) (Figure , 2b, 2c, 2d and 2e). The aliphatic peak observed between 3.81-3.32 ppm was attributed to Hb adjacent to the sulfones, while the aliphatic peak between 3.05-2.74 ppm was assigned to He, which exhibited couplings with Hd. Analysis of the C NMR spectrum revealed that the C6 position on the benzothiazole shifted from 165.7 ppm (M2, Figure ) to 175.0 ppm (P2, Figure ), indicating a modification in the chemical environment due to aryl migration. In the HMBC spectrum, the C6 clearly showed coupling with Hb, Hc, and Hd. These findings provide strong evidence for establishing the repetitive ABC (vinylbenzothiazole-olefin-sulfone) sequence.