Three lanthanide-based metal-organic frameworks, [Tb-(HMDIA)(H2O)(3)](4)center dot H2O (Tb-MDIA), [Ho(HMDIA)(H2O)(3)]center dot(H2O)(2)(Ho-MDIA), and [Nd(HMDIA)(H2O)(3)]center dot(H2O)(2) (Nd-MDIA) from the same V-shaped ligand 5,5'-methylenediisophthalic acid (H(4)MDIA), were prepared by mixing Ln(3+) and H(4)MDIA under solvothermal conditions. The crystal structures of the three complexes were determined by single-crystal X-ray diffraction. The different coordination modes of the organic ligands resulted in different framework structures among the three complexes. The luminescent properties of Ln-MDIA in the ultraviolet-visible region were also studied. Interestingly, the bright-green emitter Tb-MDIA showed high selectivity and sensitivity to allow the naked-eye visualization of Fe3+ ions and picric acid (PA) explosive, and both sensing mechanisms were revealed. Finally, Ho-MDIA and Nd-MDIA were shown to work as heterogeneous catalysts for the cyanosilylation reaction of aromatic aldehydes, and the catalysts could be recycled at least three times without any decrease in activity.