The fabrication, characterisation and controlled burst release of naphthol-functionalised micellar (NFM) nanostructures, which were grafted onto gold surfaces through cucurbit[8]uril (CB[8]) mediated host-guest interactions are described. NFMs undergo a facile change in morphology from micelles to diblock copolymers in direct response to exposure to organic solvents, including tetrahydrofuran (THF), toluene and chloroform. This induced transition in conformation lends itself to potential applications including nanocarriers for triggered burst-release of guest molecules. Nile Red was investigated as a NFM encapsulated model hydrophobic cargo inside the surface-attached micelles, which could be fully released upon exposure to THF as measured by both atomic force microscopy and UV/vis spectroscopy.