Fluorescent metal-organic frameworks (MOFs) have received great attention in sensing application. Here, we report the exploration of fluorescent MIL-53(Al) for highly selective and sensitive detection of Fe' in aqueous solution. The cation exchange between Fe3+ and the framework metal ion Al3+ in MIL-53(Al) led to the quenching of the fluorescence of MIL-53(Al) due to the transformation of strong-fluorescent MIL-53(Al) to weak-fluorescent MIL53(Fe), allowing highly selective and sensitive detection of Fe3+ in aqueous solution with a linear range of 3-200 mu M and a detection limit of 0.9 /4M. No interferences from 0.8 M Na+; 0.35 M K+; 11 mM Cu2+; 10 mM Ni2+; 6 mM Ca2+, Pb24, and Al3+; 53 mM Mn2+; 5 mM Co" and Cr3+; 4 mM Hg2+, Cd2+, Zn2+, and Mg2+; 3 inM Fe2+; 0.8 M Cl-; 60 mM NO2- and NO3-; 10 inM HPO42-, H2PO4-, SO32-, SO42-, and HCOO-; 8 mM CO32-, HCO3-, and C2O42-; and 5 mM CH3COO- were found for the detection of 150 mu M Fe3+. The possible mechanism for the quenching effect of Fe' on the fluorescence of MIL-53(Al) was elucidated by inductively coupled plasma-mass spectrometry, X-ray diffraction spectrometry, and Fourier transform infrared spectrometry. The specific cation exchange behavior between Fe' and the framework Al3+ along with the excellent stability of MIL-53(Al) allows highly selective and sensitive detection of Fe3+ in aqueous solution. The developed method was applied to the determination of Fe3+ in human urine samples with the quantitative spike recoveries from 98.2% to 106.2%.