A new approach was proposed for the determination of phenol in an unknown mixture by using three-dimension fluorescence coupled with second-order calibration methods based on rank annihilation factor analysis(RAFA),generalized rank annihilation factor analysis(GRAFA) and alternating trilinear decomposition(ATLD) algorithms,respectively.Fluorescence spectra were detected at consecutive time points in excitation range of 240-280 nm and emission range of 280-360 nm for each sample.Therefore,a three-way response data array was established and analyzed by second-order calibration method of trilinear decomposition.When the component number of sample was set to 2,the obtained average recoveries(AR) of phenol were 101.6%,115.6%,101.9%,and the root-mean-squared errors of prediction(RMSEP) for RAFA,GRAFA and ATLD were 0.33,1.18 and 0.15,respectively.When the component number of sample was set to 3,the obtained average recoveries of phenol were 134.2%,133.9%,107.1%,and the root-mean-squared errors of prediction for RAFA,GRAFA and ATLD were 1.61,1.80 and 0.51,respectively.The proposed method was applied in the determination of phenol in actual water samples with satisfactory results,and the associated verified experiments showed that ATLD is superior to RAFA and GRAFA.