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Stimuli-triggered disassembly of block copolymer vesicles or polymersomes has been conventionally achieved via solubility switching of the bilayer-forming block,requiring cooperative changes of most of the repeating units.Herein we report an alternative approach by incorporating hydrophobic blocks exhibiting stimuli-triggered headto-tail cascade depolymerization features.Amphiphilic block copolymers bearing this motif self-assemble into selfimmolative polymersomes(SIPsomes).