This article reports on the synthesis of thermo- and light-sensitive hydrophilic block copolymers, poly(ethylene oxide)-b-poly(ethoxytri (ethylene glycol) acrylate-co-o-nitrobenzyl acrylate), and the study of their micellization/dissociation transitions in water in response to temperature changes and UV irradiation. The block copolymers with controlled molecular weights and narrow polydispersities were synthesized by atom transfer radical polymerization of a mixture of ethoxytri (ethylene glycol) acrylate and o-nitrobenzyl acrylate with a molar ratio of 100: 10 from a PEO macroinitiator. Dynamic light scattering and fluorescence spectroscopy studies showed that these copolymers were molecularly dissolved in water at lower temperatures and self-assembled into micelles with the thermosensitive block associating into the core and the PEO block forming the corona when the temperature was above the lower critical solution temperature (LCST) of the thermosensitive block. Upon UV irradiation, the o-nitrobenzyl group was cleaved and the LCST of the thermosensitive block was increased, causing the dissociation of micelles into unimers and the release of encapsulated fluorescent dye Nile Red into water. Further increasing the temperature induced the formation of micelles again and the re-encapsulation of Nile Red. The thermo-induced formation and dissociation of micelles were reversible.