Despite the fact that effective photosensitizers (PSs) can be achieved through rational molecular design, controlling the hierarchical assemblies of individual PSs with distinct function and morphological nanoscopic architectures remains a challenge. Here, very ordered one-dimensional PS polymers and their hollow tubular structures are presented from aqueous assembly of organic PS-based di- or tri-blocked supramolecules. Di-blocked PSs were interdigitated into 1D fibrils, significantly quenching photooxidation. Meanwhile, tri-blocked PSs were tilted with respect to each other to generate hollow tubules, showing remarkable photo-activities as well as photo-stability, which are particularly suited for green chemistry due to their unusual rapid photo-oxidation.