Botryoid-shaped reactive terpolymer nanoparticles, whose aldehyde-functional living domains are miniaturized into small-sized discrete grapes and attached onto the outwardly-branched scaffolds of fluorinated segments, are reported. These nanostructures can be fabricated by spontaneous structural reorganization of core-shell terpolymer micelles simply by manipulating drying conditions. The miniaturized discrete living domains are stabilized by outwardly-branched scaffolds and exhibit excellent accessibility to solution media, thus can effectively respond to solution media, which is desired in sensor-related applications.