AbstractIn this contribution, a new Schiff‐base hybrid cross‐linked polymer (TFPT‐SHCP) derived from triazine derivatives and silsesquioxanes was developed, and its photocatalytic performance was systematically investigated. Compared with traditional organic Schiff base catalysts, in TFPT‐SHCP, organic inorganic hybrid silsesquioxanes monomers at the molecular level can serve as a sturdy host backbone, bringing structural ultrastability to the final material. And their excellent strength and durability make them have good application prospects in water treatment. Furthermore, the introduction of triazine derivatives with excellent photoelectric performance and the construction of −C=N‐ result in excellent photocatalytic performance of TFPT‐SHCP. The as‐prepared TFPT‐SHCP exhibits excellent degradation capacity of various organic pollutants under visible light catalysis, with degradation rate constants for Congo Red (CR), rhodamine B (RB) and tetracycline hydrochloride (TH) reaching 0.302 min−1, 0.121 min−1, 0.161 min−1, respectively. Under simulated outdoor conditions, dye solutions with concentrations up to 500 ppm can be degraded to complete decolorization within 5 weeks. This work demonstrates the enormous potential of POSS‐based Schiff base materials as a platform for visible light catalysts, paving the way for the pre design and functionalization of related materials in the future.