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A porous ball-flower-like Co₃O₄/Fe₂O₃ heterostructural photocatalyst was synthesized via a facile metal–organic-framework-templated method, and showed an excellent degradation performance in the model molecule rhodamine B under visible light irradiation. This enhanced photocatalytic activity can be attributed to abundant photo-generated holes and hydroxyl radicals, and the combined effects involving a porous structure, strong visible-light absorption, and improved interfacial charge separation. It is notable that the ecotoxicity of the treated reaction solution was also evaluated, confirming that an as-synthesized Co₃O₄/Fe₂O₃ catalyst could afford the sunlight-driven long-term recyclable degradation of dye-contaminated wastewater into non-toxic and colorless wastewater.