Herein, we report a feasible method to prepare a tadpole-shaped PEG-POSS-(Azo)7 polymer. The polymer self-assembled into a large vesicle in aqueous solution, undergoing reversible smooth-curling transformation responsive to UV and dark conditions. Incorporating POSS units into the azopolymer furnished quick trans-cis isomerization along a cubic orientation. The orientational isomerization formed some pores on the vesicular membrane and endowed the highly sensitive photoresponsive property. Encapsulation of various fluorescent dyes affected the hydrophilic/hydrophobic ratio of self-assemblies, causing their morphological transition from vesicles to micelles. Response to UV irradiation, the quick trans-cis isomerization resulted in rapid release of the encapsulated dyes. The intriguing photoresponsive property renders this kind of tadpole-shaped POSS hybrid azopolymer a potential for application in controlled release of drug.