Allura red, sunset yellow, tartrazine and caramel are food colorants and they have well defined potentiometry because of their phenolic structures. The assay of mixture containing food colorants were executed with potentiometry without any chemical separation. The multivariate calibration technique was applied to simultaneous determination of the food colorants in food sample. This method is principal component regression (PCR). The mixture of colorants (alone or mixture) were titrated by potassium hydroxide potentiometry. The linear relationship between the volumes of titrant and the concentrations of analytes was obtained by chemometric method. PCR calibration in the range of 0.6 to 2.2 mL of the potentiometric method for the calibration set was prepared in the range Delta lambda= 0.05 mL values were read at intervals. In the next step, PCR method, commercial beverage sample caramel, allura red, tartrazine and sunset yellow quantity determinations were performed at the same time. PCR calculated from experimental data, calibration method, a good fit between the observed and the results were compared statistically.