In order to promote the classification ability of the traditional time-resolved LIF technique to achieve oil spill detection, a novel LIF polarization experimental setup was developed in the laboratory with the ability to obtain time-resolved LIF spectra of both the Co-polarized and Cross-polarized components simultaneously under linearly excitation. With it, a series of oil spills investigation were performed with six crude oil samples, which were carefully selected to ensure each two of them are derived from adjacent wells located within the same well block. After recording of a complete series of time-resolved LIF spectral data, the polarization direction of the excitation was rotated by 90 degrees to proceed with acquisition of another series of data. And with these two sets of data, LIF spectra of the two orthogonal polarization components were calibrated to guarantee the accuracy of the polarization detection. Spectral data of the two orthogonal polarization components were processed with the newly proposed intensity-normalized method and combined to form the data array, based on which clustering and classification results were obtained via the approach of PCA. It was showed that no matter within the three-dimensional space nor the two-dimensional plane composed of the principal components, ideal clustering results can be obtained from similar crude oil samples based on time-resolved LIF polarization technique, even though their locations of fluorescence peak intensities were quite close. Compared with the classification results achieved with the traditional time-resolved LIF technique based on the same data set, it can be concluded that with the auxiliary help of the distinct LIF polarization characteristics of different oil, the classification ability of time-resolved LIF technique is significantly improved.