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Pickering emulsions are an excellent platform for interfacial catalysis. However, developing simple and efficient strategies to achieve product separation and catalyst and emulsifier recovery is still a challenge. Herein, we report the reversible transition between emulsification and demulsification of a light‐responsive Pickering emulsion, triggered by alternating between UV and visible light irradiation. The Pickering emulsion is fabricated from Pd‐supported silica nanoparticles, azobenzene ionic liquid surfactant, n‐octane, and water. This phase behavior is attributed to the adsorption of azobenzene ionic liquid surfactant on the surface of the nanoparticles and the light‐responsive activity of ionic liquid surfactant. The Pickering emulsion can be used as a microreactor that enables catalytic reaction, product separation as well as emulsifier and catalyst recycling. Catalytic hydrogenation of unsaturated hydrocarbons at room temperature and atmospheric pressure has been performed in this system to demonstrate product separation and emulsifier and catalyst re‐use.

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