We report stimuli-triggered fabrication of polymersomes from water-in-oil-in-water (W/O/W) multiple double emulsion droplets and the dual-stimuli (temperature and UV) responsive behavior of corresponding polymersomes. The polymersome comprises Tween20, cholesterol; and poly(styrene)block-poly(N-isopropylacrylamide-co-spironaphthoxazine methacryloyl), i.e., PS-b-P(NIPAAm-co-SPO), synthesized by stepwise reversible addition fragmentation chain transfer (RAFT) polymerization. Amphiphilic PS-b-P(NIPAAm-co-SPO) copolymer forms micelles in water above the critical micelle concentration (CMC) of 0.7 g/L at 23 degrees C. The micelles show a temperature-driven aggregation among the micelles above 30.6 degrees C, confirmed by a decrease in UV-vis transmittance. The micelles also show a color change without colloidal instability under 365 urn UV at room temperature. PS-b-P(NIPAAm-co-SPO) plays not only a role of the polymeric surfactant in the preparation of W/O/W multiple double emulsions but also an important role in the stimuli-triggered transformation from multi- to single-core double emulsion droplets under heat and UV light irradiation. It was found that the morphological transformation of W/O/W multiple double. emulsions by UV irradiation was Much faster than temperature change. Dual-responsive polymersomes were simply prepared after solvent removal and they exhibit stable and reversible size and color variations under temperature and UV visible changes, respectively.