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The synthesis of well-defined and light-responsive block copolymers containing vinyl naphthol (VN) as photoacidic comonomer via RAFT is presented. This specific photoacid has been identified in earlier work as highly photostable and we therefore incorporate different amounts of VN in combination with styrene and 2-vinylpyridine as proton acceptor. After studying the terpolymerization using two different chain transfer agents, we prepared amphiphilic block copolymers and studied their micellization in water as selective solvent.We could show that the resulting core-corona micelles can be used to perform light-triggered release of an encapsulated model cargo (Nile Red) and even two-color dynamic light scattering could be used to monitor changes in aggregate size under illumination. We see great potential for these materials in controlled drug delivery and other fields where spatial and temporal control over macromolecular conformation and net charge or charge density is an advantage.