Pickering emulsion-based photocatalysis is considered to be a promising system due to its large active surface area and water/oil spatial separation capability for enrichment of substrates and products. In this work, a novel hierarchical structure composed of calcium alginate gel sphere wrapped ionic liquid-inwater Pickering emulsion with TiO2 in the water phase, which are stabilized by graphene oxide, is prepared via a facile one-step emulsion gelation method. Such subtle combination of Pickering emulsion, hydrogel and TiO2 with a multi-stage solid-liquid assemblage structure shows enhanced degradation activity of 2-naphthol into small molecular alkanes under simulated solar irradiation. The photodegradation activity is attributed to the ionic liquid as adsorption medium for 2-naphthol, and the high-efficient charge separation at graphene oxide/TiO2 interface superior to that of pure TiO2. More importantly, the as-prepared millimeter-sized assembled gel spheres can be directly used as the column filler to construct continuous flow photocatalytic system, maintaining the promising performance in removing pollutants from water with similar to 100% remove ability of 2-naphthol on stream. A charge transfer mechanism of the photocatalyst is proposed, i.e. photogenerated charges are separated in TiO2/graphene oxide p-n heterostructure at the interface of Pickering emulsion droplets. (C) 2021 Elsevier Inc. All rights reserved.