hydrogen bonding, [19] π-π interaction, [20] host-guest interactions. [21,22] For example, Kim and co-workers reported the strategy to promote phosphorescence emission by using direct heavy atom effect (halogen and hydrogen bonding). [23] Zhao and coworkers presented a novel strategy to achieve color-tunable ultralong organic RTP by conjugating different phosphorescence emitting agents onto a polymer backbone. [24] In particular, host-guest interactions have proven to be an accessible approach in achieving RTP emission both in solid-and solution-phase. [25,26] Host macrocyclic molecules with robust cavities, such as cyclodextrins [27] and cucurbiturils, [28] can provide a molecular vibration-limited microenvironment to inhibit the non-radiative relaxation decay of the phosphor and prevent excited triplet state from being quenched by oxygen or water. Our group previously reported an efficient solid-state RTP supermolecule enhanced by cucurbit[6]uril, which increased the phosphorescence quantum yield of 4-bromophenylpyridinium salt from 2.6% to 81.2%. [29] Notably, RTP materials in solution-phase are of particular interest for timeresolved biological imaging because of its unique character that it can be feasibly distinguished from the autofluorescence and background fluorescence in cellular biospecies. [30][31][32] However, the excited triplet state of phosphor tends to occur non-radiative relaxation decay caused by dissolved oxygen and water, so developing purely organic RTP systems in aqueous solution is still limited, especially with NIR emissive performance.Artificial light-harvesting systems (LHSs) are expectantly fabricated to mimic natural photosynthesis process for more efficient utilization of light energy, which are usually characterized by high donor/acceptor ratio to ensure that large amounts of donors transfer energy to one acceptor. [33][34][35] Supramolecular self-assembly turns out to be a practicable approach to build LHSs through the encapsulation of the chromophores to enhance corresponding luminescence and avoid self-quenching effect. [36,37] Supramolecular LHSs can be conveniently obtained by mixing relevant building units driven by noncovalent interactions. [38] Cucurbit[8]uril (CB[8]), as a unique macrocyclic compound with stiff cavity, has been capable of accommodating charge-transfer complexes to form stable host-guest pairs, which can be utilized to design supramolecular-organic The construction of highly effective phosphorescence energy transfer capturing system still remains great challenge in aqueous phase. Herein, a high-efficiency supramolecular purely organic room temperature phosphorescence (RTP)-capturing system via a secondary assembly strategy by taking advantage of cucurbit[8]uril (CB[8]) and amphiphilic calixarene (SC4AH) is reported. Comparing with free bromonaphthalene-connected methoxyphenyl pyridinium salt (G), G⊂CB[8] exhibits an emerging RTP emission peak at 530 nm. Moreover, G⊂CB[8] further interacts with SC4AH to form the ternary assembly G⊂CB[8] @ SC4AH accompanied by...