The biodiesel containing fatty acid methyl esters (FAMEs) are blended with refined diesel products. Here, we evaluate relative FAME composition ratio as a potential index to discriminate the pollution origin in diesel-contaminated soil. Artificially contaminated soil was prepared to mimic the release of petroleum products using four different refined diesels; in addition, the contaminated soil was put under natural weathering conditions. The variations in the relative FAME composition ratio was compared with those of the corresponding diesel origin using principal component analysis (PCA) for 60 days. All soil samples could be classified into four groups according to diesel origin using two principal components. The proposed method can be used to discriminate the specific diesel pollution origin in contaminated soils.