The characterization of complex hydrocarbon mixtures remains a challenging task. Advances in analytical characterization have been made in several fronts. One such advance is in gas chromatography-vacuum ultraviolet spectrometry (GC-VUV), which allows for sensitive, universal detection that is particularly well suited for characterizing petroleum and petroleum products. As complete VUV (125-430 nm) spectra are obtained continuously, there are advantages in being able to arrange and visualize data in a multidimensional way through a plot of elution time versus wavelength and absorption intensity, providing a new method of two-dimensional separation, namely, GC x VUV. All structural features are readily visualized in a manner complementary to two-dimensional gas chromatography, GC x GC. In this study, we demonstrate the advantages of the GC x VUV approach by comparing the analysis of a diesel sample to results obtained by GC-FID, GC-VUV, and GC x GC-FID.