The synthesis of polystyrene-block-poly[2-(N-morpholino)ethyl methacrylate] (PS-b-PMEMA) as a new highly amphiphilic and multiple stimuli-responsive block copolymer is presented. To achieve high molecular weights far beyond 100 kDa in a highly controlled manner (dispersities < 1.1), a synthetic route via sequential combination of anionic polymerization for the PS block and reversible addition-fragmentation chain transfer (RAFT) polymerization for the PMEMA block is used. The synthesized block copolymers are investigated regarding their microphase separation in bulk, which delivers well-ordered self-assembled bulk structures as evidenced by small-angle x-ray scattering (SAXS) and atomic force microscopy (AFM). In aqueous solution, the block copolymer self-assembles into narrowly size distributed micelles with a PMEMA corona. The stimuli-triggered micelle response towards temperature, pH, and kosmotropic as well as chaotropic salts is shown via various dynamic light scattering (DLS) experiments. Furthermore, a dependency of aggregate size on solvent composition in polymer/ tetrahydrofuran/water mixtures is described. The reported findings deliver a feasible pathway to high molecular weight block copolymers with tailored chemical properties and show the potential of PS-b-PMEMA as material for mechanically demanding switchable devices. (C) 2016 Elsevier Ltd. All rights reserved.