Covalent organic frameworks (COFs) are porous crystals of high potential in biomedical applications. The chemical bonds within COF structures are critical for the overall therapeutic performance. Here, the design and synthesis of radioactive COF are reported by introducing labile diselenide bonds into the structure backbone. This diselenide bonded COF, PorSe-CuPt, constructed from Cu and Pt ion porphyrin units, is capable of bond cleavage upon irradiation, thus releasing the drug molecule, CBL0137, carried in the pores. Concerted with the promotion of X-ray absorption by Pt