A spectrofluorometric method for the quantitative determination of flufenamic, mefenamic and meclofenamic acids in mixtures has been developed by recording emission fluorescence spectra between 370 and 550 nm with an excitation wavelength of 352 nm. The excitation-emission spectra of these compounds are deeply overlapped which does not allow their direct determination without previous separation. The proposed method applies partial least squares (PLS) multivariate calibration to the resolution of this mixture using a set of wavelengths previously selected by Kohonen artificial neural networks (K-ANN). The linear calibration graphs used to construct the calibration matrix were selected in the ranges from 0.25 to 1.00 mug ml(-1) for flufenamic and meclofenamic acids, and from 1.00 to 4.00 mug ml(-1) for mefenamic acid. A cross-validation procedure was used to select the number of factors. The selected calibration model has been applied to the determination of these compounds in synthetic mixtures and pharmaceutical formulations.