Abstract Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-TOFMS) was used for the characterization of aromatic compounds present in extra heavy gas oil (EHGO) from Brazil. Individual identification of EHGO compounds was successfully achieved in addition to group-type separation on the chromatographic plane. Many aromatic hydrocarbons, especially polycyclic aromatic hydrocarbons and sulfur compounds, were detected and identified, such as chrysenes, phenanthrenes, perylenes, benzonaphthothiophenes and alkylbenzonaphthothiophenes. In addition, triaromatic steroids, methyl-triaromatic steroids, tetrahydrochrysenes and tetraromatic pentacyclic compounds were present in the EHGO aromatic fractions. Considering the roof-tile effect observed for many of these compound classes and the high number of individual compounds identified, GC × GC-TOFMS is an excellent technique to characterize the molecular composition of the aromatic fraction from EHGO samples. Moreover, data processing allowed the quantification of aromatic compounds, in class and individually, using external standards. EHGO data were obtained in μg g −1, e.g., benzo[a]pyrene were in the range 351 to 1164 μg g −1. Thus, GC × GC-TOFMS was successfully applied in EHGO quantitative analysis.