Comprehensive two-dimensional gas chromatography (GC × GC) coupled to time-of-flight mass spectrometry is a powerful separation tool for complex petroleum product analysis. However, the most commonly used electron ionization (EI) technique often makes the identification of the majority of hydrocarbons impossible due to the exhaustive fragmentation and lack of molecular ion preservation, prompting the need of soft-ionization energies. In this study, three different soft-ionization techniques including photo ionization (PI), chemical ionization (CI), and field ionization (FI) were compared against EI to elucidate their relative capabilities to reveal different base oil hydrocarbon classes. Compared with EI (70 eV), PI (10.8 eV) retained significant molecular ion (M +· ) information for a large number of isomeric species including branched-alkanes and saturated monocyclic hydrocarbons along with unique fragmentation patterns. However, for bicyclic/polycyclic naphthenic and aromatic compounds, EI played upper hand by retaining molecular as well as fragment ions to identify the species, whereas PI exhibited mainly molecular ion signals. On the other hand, CI revealed selectivity towards different base oil groups, particularly for steranes, sulfur-containing thiophenes, and esters, yielding protonated molecular ions (M + H) + for unsaturated and hydride abstracted ions (M-H + ) for saturated hydrocarbons. FI, as expected, generated intact molecular ions (M +· ) irrespective to the base oil chemical classes. It allowed elemental composition by TOFMS with a mass resolving power up to 8000 (FWHM) and a mass accuracy of 1 mDa, leading to the calculation of heteroatomic content, double bond equivalency, and carbon number of the compounds. The qualitative and quantitative results presented herein offer a unique perspective into the detailed comparison of different ionization techniques corresponding to several hydrocarbon classes., (© 2018 John Wiley & Sons, Ltd.)