To investigate the specific strategy for sequence regulation with living anionic polymerization, three sequence-defined polymers with similar number of SiH functional groups per chain but totally different periodicities which distributed as gradient, tandem, and symmetrical structures were synthesized. Through different feeding methods and coupling reaction after polymerization during the living anionic copolymerization of styrene (St) and dimethyl-[4-(1-phenylvinyl)phenyl]silane (DPE-SiH), the synchronous regulation of monomer sequence and functionalized block periodicity in polymer chains was successfully achieved. The monomer sequence distributions in these three structures were confirmed by in situ 1H NMR. As the monomer sequence and block periodicity are synchronously regulated, this effort could promote the further development of the sequence regulation and the design of novel functionalized polymers with living anionic polymerization method, and the strategy we investigated also can improve the nov...