The development of intelligent nano-platforms with high tumor-targeting capability, enhanced solubility, and efficacious photochemotherapy is urgently demanded for clinical anticancer treatments. Herein, we report an amphiphilic porphyrin (P) to complex with camptothecin (CPT) to form supra-amphiphile-assembled nanoparticles (CPT@P). The host–guest complexation between P and CPT promotes the singlet oxygen production of P and enhances the solubility of CPT, which should be beneficial to improve PDT efficiency and chemotherapy effect. Cancer cell membrane (M) is further used to camouflage CPT@P, which endows the resulting CPT@P"M with excellent stability, homologous targeting ability, and specific co-delivering of the chemotherapeutic drug and photosensitizer to tumor cells. The presented work takes advantage of the unique structure and intrinsic performance of P to construct an integrative co-delivery system with the assistance of membrane-coating technology, which not only extends the application scopes of porphyrin photosensitizers but also provides a promising nanoplatform for cancer therapy.