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Chemometric methods have unique advantages regarding comprehensive consideration of multiple parameters and the classification of samples or variables. Classification of oil spill sources was carried out by using chemometric techniques, such as Repeatability Limit, hierarchical cluster analysis (HCA), Student's t -test and Principal component analysis (PCA) Biplot. In addition, this paper takes the fingerprint identification of a Dalian "7.16″ oil spill accident as an example to illustrate the effectiveness of chemometric techniques in oil identification. PCA scores plot (explaining 82.77% of variance accounted for three PCs) showed that samples belong to four clusters and result of HCA method further confirmed that. The residual oil in Jinshatan Beach and Haibei Square may be caused by the explosion of Dalian "7–16" oil pipeline accident. The use of chemometric techniques is significant in providing independent validation for classifying the types of spilled oil in the investigation of oil spill pollution. The results will be of great significance to improve the accuracy and efficiency of oil spill identification based on oil fingerprint. • Origin based classification of oil residue by GC-MS and chemometrics method. • Multivariate and multiway analysis are mainly used in oil fingerprint methods. • Dalian "7.16″ oil spill accident provide a case platform for chemometric techniques. • It involved a principal component and hierarchical cluster analysis. [ABSTRACT FROM AUTHOR]