New thermoresponsive polydisulfides of POEOMA multiblocks linked with disulfide bonds having redox-responsive properties are reported. These POEOMA-multisegmented polydisulfides were synthesized by a new method employing a combined RAFT/aminolysis and reversible thiol-disulfide redox reaction that centers on the synthesis of new disulfide-labeled difunctional RAFT agent. RAFT polymerization proceeded in living fashion, yielding well-defined POEOMA copolymers with middle disulfides and terminal RAFT species. They were then used as precursors for thiol-disulfide polyexchange induced by aminolysis and reductive reaction followed by oxidation: these polydisulfides with different molecular weights and end groups ex hibited tunable thermoresponsive properties and thiol-responsive degradation.