Abstract: | Phototheranostic nanoplatforms are of particular interest for cancer diagnosis and imaging‐guided therapy. Herein, we develop a supramolecular approach to fabricate a nanostructured phototheranostic agent through the direct self‐assembly of two water‐soluble phthalocyanine derivatives, PcS4 and PcN4. The nature of the molecular recognition between PcS4 and PcN4 facilitates the formation of nanostructure (PcS4‐PcN4) and consequently enables the fabrication of PcS4‐PcN4 with completely quenched fluorescence and reduced singlet oxygen generation, leading to the high photoacoustic and photothermal activity of PcS4‐PcN4. In vivo evaluations suggest that PcS4‐PcN4 could not only efficiently visualize a tumor with high contrast through whole‐body photoacoustic imaging but also enable excellent photothermal therapy for cancer. |