Metal–organic cage photocatalysts with nanoscale dimensions have received wide attention in the field of photocatalytic environmental pollutant treatment due to their large cavities, easy modification, high tunability, and enriched active sites. Herein, we prepared a series of dihydroanthracene-cored terpyridine-based metallo-cuboctahedron nanomaterials through a self-assembly method, which exhibited satisfactory degradation performance for persistent organic pollutants under visible light irradiation. In particular, under light conditions, S1-Zn, one of the prepared nanomaterials, produced photogenerated holes oxidizing water molecules to ∙OH, which attacked ibuprofen (IBU) for up to 95% degradation. Simultaneously, the corresponding photogenerated electrons reduced the dissolved oxygen in water, producing 66.2 μmol/L hydrogen peroxide. The obtained supramolecular photocatalytic materials have a stable structure with non-precious metals and do not require a sacrificial agent. The metal sites of metallo-cuboctahedrons adsorb pollutants and transfer captured holes to them, accelerating degradation and promoting simultaneous H₂O₂ production. This work not only proposes a simple and efficient synthesis method for supramolecular photocatalysts but also opens up opportunities for efficient, low-cost, and multifunctional materials for environmental persistent organic pollutants treatment.