Oil pollutants are one of the main factors that endanger the ecological environment. The accurate identification and measurement of mixed oil pollutants is of great significance for environmental monitoring. In view of the serious overlap of spectral components of mixed oil pollutants, it is difficult to distinguish them by chemical methods. In this study, three-dimensional fluorescence spectrum combined with alternating residuals trilinearization (ART) algorithm is adopted to detect oil pollutants. ART algorithm is an improvement of parallel factor algorithm without presetting factor number. A three-dimensional fluorescence spectrum detection system was built to study the three-dimensional fluorescence spectrum characteristics of 0 # diesel oil, 97 # gasoline and kerosene. 30 groups of SDS micelle solutions of 0 # diesel oil, 97 # gasoline and kerosene were configured, and three-dimensional fluorescence spectral data were obtained. The three-dimensional fluorescence spectrum data of mixed oil pollutants after scattering elimination were analyzed by ART algorithm. The experimental results show that the ART algorithm is effective for 0# diesel, 97# gasoline and kerosene. The average recovery rates of gasoline and kerosene are 103. 6%, 97. 32%, and 99. 86%, respectively. The spectra of the three components obtained by ART algorithm are in good agreement with the real spectrum. Both qualitative and quantitative analysis show that the threedimensional fluorescence spectrum combined with ART algorithm is an effective method for the detection of oil pollutants.