In Tris-HCl buffer (pH ¼ 7.43), Tb 3þ can react with oxolinic acid (OA) and form a 1:2 complex, which emits the intrinsic fluorescence of Tb 3þ . Based on this, a new fluorimetric method of determination of OA is developed. Under the optimum conditions, the enhanced fluorescence intensity of the system is proportional to the concentration of OA in the range of 1.5 Â 10 27 2.5 Â 10 25 mol/L, and the detection limit is 5.5 Â 10 29 mol/L. Recovery test was also satisfactory. The experiments indicated that the luminescence mechanism was attributed to the M Ã -M luminescence.