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© 2020 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim.Here we present an"immortal" N -(diphenylphosphanyl)-1,3-diisopropyl-4,5-dimethyl-1,3-dihydro-2H -imidazol-2-imine/diisobutyl (2,6-di-tert-butyl-4-methylphenoxy) aluminum (P(NIiPr)Ph2/(BHT)AliBu2)-based frustrated Lewis pair (FLP) polymerization strategy for rapid and scalable synthesis of the sequence-controlled multiblock copolymers at room temperature. Without addition of extra initiator or catalyst and complex synthetic procedure, this method enabled us to achieve a tripentaconta