We report the photocontrollable micelle–cluster transition of an ABC-type triblock copolymer in an ionic liquid (IL). Polystyrene-b-poly(ethylene oxide)-b-poly(4-phenylazobenzyl acrylamide-r-N-isopropylacrylamide) (PSt-b-PEO-b-P(AzoBnAm-r-NIPAm)) was synthesised, where PSt is IL-phobic, PEO is IL-philic, and P(AzoBnAm-r-NIPAm) is photo- and thermoresponsive in the IL. At high temperatures, the triblock copolymer forms micelles with PSt cores; furthermore, at low temperatures, micelles self-assemble into clusters induced by the aggregation of P(AzoBnAm-r-NIPAm). Under UV irradiation, the micelles form clusters at lower temperatures than that in the dark because of the change in the solubility of P(AzoBnAm-r-NIPAm) induced by photoisomerisation of the azobenzene groups, indicating that this triblock copolymer has a photocontrollable micelle–cluster transition temperature.
