A multifunctional lanthanide metal–organic framework: Tb(cpioa) was successfully obtained by a facile hydrothermal method. Based on the single-crystalline XRD, BET and FT-IR characterizations, it’s found that Tb(cpioa) has a porous 3D networks crystal structure. Luminescent characteristics and sensing properties of Tb(cpioa) were investigated in details. Tb(cpioa) has a specific and sensitive recognition capability of acetone, Fe³⁺ and Cr₂O₇^2- in water. Based on detailed characterizations and theoretical computations, the luminescence quenching mechanism is found complicated and composed of four quenching processes: the competition of UV–vis absorption, the weak interactions between ligand and analytes, and two dynamic transfer processes: the fluorescence resonance energy transfer (FRET) and the photo-induced electron transfer (PET).