Due to the strong overlapping of absorption spectra, the simultaneous determination of four food pigments mixtures (amaranth, carmine, enticed red, pyrosine) by using spectrophotometric Method is difficult. A chemometrics method, partial least squares (PLS), was described for the simultaneous determination of four pigments in synthetic samples. Spectra of mixtures of four food pigments between 380-640 nm wavelengths by 0.2 nm intervals were recorded, in the range of concentrations comprised between 1-8 mu g mL(-1) for amaranth, carmine, enticed red and 0.5-4 mu g mL(-1) for pyrosine, respectively. The analyte recoveries from synthetic mixtures range from 100.26 to 103.24 % for amaranth, from 93.677 to 113.03 % for carmine, from 95.749 to 99.448 % for enticed red and from 85.446 to 104.33 % for pyrosine, respectively. The root mean square difference (RMSD) for the four analytes/are 0.052772, 0.079997, 0.088947, 0.061912, respectively. The result shows that PLS is an efficient chemometrics method applied for prediction of the-four analytes.