A novel orthogonal supramolecular polymer (Q[10]-TPDPB-Lu 3+ ) in a host-guest ratio of 2:1 was successfully constructed utilizing the specificity and excellent cavity matching of Q[10] with the tripyridine derivatives (TPDPB). Significantly, non-covalent interactions between Q[10]'s hydrophobic cavities and Lu 3+ were used to induce charge transfer of TPDPB to TPDPB and TPDPB to Lu 3+ , resulting in the construction of structurally interesting orthogonal assemblies with excellent fluorescence properties. Finally, the Q[10]-TPDPB-Lu 3+ assemblies were shown to have good recognition and classification of strong and weak acid anions as well as iodide anions, and the classification was accompanied by a clear fluorescence emission change allowing visual observation.