Since phenolic pollutants and organic dyes do great harm to the environment and human health, it is necessary to explore efficient and low-cost methods to monitor and adsorb them respectively. Herein, a multivalent supramolecular assembly composed of triphenylamine derivatives (TPAN) and nor-seco-cucurbit[10]uril (ns-Q[10]) was designed and synthesized. The supramolecular assembly has a luminescent core and cationic N-methyl imidazole groups connected by alkyl chains, and triphenylamine derivatives (TPAN) can be combined with ns-Q[10] in a stoichiometric ratio of 2:3 to form a network multivalent assembly with yellow fluorescence enhancement. At the same time, this supramolecular assembly has been applied to supramolecular recognition of 4-Hydroxyphthalonitrile (4-HP) and Eosin Y (ESY), and it can also adsorb and remove ESY in aqueous solution. This shows that the multivalent supramolecular assembly shows good potential in industrial applications such as the emission of phenolic pollutants and the adsorption of organic dyes.