A facile solvothermal epitaxial growth combined with a mild oxidation route has been developed for the fabrication of a magnetically recyclable Fe3O4/WO3 core–shell visible‐light photocatalyst. In this core–shell structured photocatalyst, visible‐light‐active WO3 nanoplates (the shells) with high surface area are used as a medium to harvest absorbed photons and convert them to photogenerated charges, while conductive Fe3O4 microspheres (the cores) are used as charge collectors to transport the photogenerated charges. This is a new role for magnetite. The Fe3O4/WO3 core–shell structured photocatalysts possess large surface‐exposure area, high visible‐light‐absorption efficiency, stable recyclability, and efficient charge‐separation properties, the combination of which has rarely been reported in other visible‐light‐active photocatalysts. Photoelectrochemical investigations verify that the core–shell structured Fe3O4/WO3 has a more effective photoconversion capability than pure WO3 or Fe3O4. At the same time, the visible‐light photocatalytic ability of the Fe3O4/WO3 photocatalyst has significantly enhanced activity in the photodegradation of organic‐dye materials. The results presented herein provide new insights into core–shell materials as high‐performance visible‐light photocatalysts and their potential use in environmental protection. Tungsten‐clad iron: A solution epitaxial growth method has been developed for the fabrication of Fe3O4/WO3 photocatalysts. The core–shell structured photocatalysts (see picture) possess large surface‐exposure area, high light‐absorption efficiency, stable recyclability, and efficient charge‐separation properties, which lead to its significantly enhanced photoelectrochemical and photocatalytic activities.