By using a cyclotriveratrylene‐based ligand 5,12,19‐trimethoxy‐6,13,20‐tricarboxy‐methoxy‐cyclotriveratrylene (H3L), four lanthanide‐based compounds, Eu(L)(DMF)2 (1), Tb(L)(DMF)2 (2), Gd(L)(DMF)2 (3), and Yb(L)(DMF)(H2O) (4), have been constructed. Compounds 1–3 are isostructural and show charming two‐bowl interlocked chains linked by L3– anions and Ln3+ cations. The chains are further linked by C–H···π interactions to form two‐dimensional supramolecular layers, respectively. In 4, L3– anions bridge Yb3+ ions to yield a fascinating three‐dimensional framework. The compounds are characterized by IR and powder X‐ray diffraction. Their solid UV/Vis spectra and fluorescence properties are also studied. By fluorescence detection of metal cations, anions, and organic small molecules, compounds 1 and 2 exhibit high selectivity and sensitivity to Fe3+ ions, MnO4– anions, and nitromethane by quenching processes.