Multicompartment vesicles of ferrocene-containing triblock terpolymer containing on-off switchable pores in the vesicular membrane are prepared by seeded RAFT polymerization. In these multicompartment vesicles, the incompatible solvophobic poly(4-vinylbenzyl ferrocenecarboxylate) (PVFC) and poly(benzyl methacrylate) (PBzMA) blocks form the porous phase-segregated membrane and the solvophilic poly[2-(dimethylamino) ethyl methacrylate] block locates at the inner and outer sides of the membrane. These porous multicompartment vesicles are redox-responsive and the membrane pores can be on-off switched through redox triggering. These porous multicompartment vesicles are deemed to be new nanoassembly of ABC triblock terpolymer and are anticipated to be a smart host to load and release guests.