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We synthesized a new water‐soluble tribenzotriquinacene‐based hexacarboxylate (TBTQ‐C6, or H) which can associate with an azobenzene‐containing amphiphile (trans‐AZO) to form the H ⊃ trans‐AZO supra‐amphiphile by host‐guest interactions in water. This supra‐amphiphile further self‐assembles into photo and pH dual‐responsive vesicles. The reversible conversion between the vesicles and micelles can be easily controlled by both UV or visible light irradiation and pH adjustment. This work represents the first study of stimuli‐responsive TBTQ‐based supramolecular vesicles, which may have potential applications in various fields such as controlled drug delivery systems.