Catalyzed light olefin oligomerization is widely used in petrochemical industries to produce fuels and chemicals. Light olefins such as propene and butenes are commonly selected as feedstocks. Solid phosphoric acid (SPA) and zeolite are representative acidic catalysts. Both the feedstocks and catalysts have an impact on the product composition. In this study, state-of-the-art instrumentation two-dimensional gas chromatography (GC × GC) coupled photoionization─time of flight mass spectrometry was employed to investigate the composition of dodecene products produced from olefin oligomerization. Information such as the olefin congener distribution, dodecene structural subgroup distribution, and individual dodecene isomers was obtained and utilized in the statistical analyses. By using specific data sets of the product composition, the distinguishment between SPA and zeolite catalysts as well as among the feedstocks was achieved by applying the unsupervised screening approaches (principal component analysis and hierarchical clustering analysis). The potential indicators of catalysts and feedstocks were selected by the feature selection methods (univariate analysis: analysis of variance and multivariate analysis: partial least squares-discriminant analysis).