It is difficult to determine the mixtures of phenol, m-cresol and thymol directly by routine analytical method since their fluorescent spectra are overlapped closely. Excitation-emission matrix fluorescence technology combined with parallel factor (PARAFAC) algorithm is used to determine phenol, m-cresol and thymol simultaneously. Results show that the concentrations of phenol and thymol resolved by PARAFAC are better than the actual one when three compounds are determined simutaneously, and the average recoveries are (95.23±2.55)% and (102.8±1.97)% respectively. However, the result of m-cresol is not satisfied, and the resolved concentration deviates from the actual one severely. Moreover, two component compounds mixed with each other among phenol, m-cresol and thymol are also studied, and the result is better than that obtained in the mixtures contained all of three phenolic compounds. In addition, the accuracy of the PARAFAC algorithm is also evaluated through figures of merit. The method using excitation-emission fluorescence combined with PARAFAC algorithm can determine phenol, m-cresol and thymol simultaneously with a good selectivity, and the limit of detection achieves to 1 μg/L.