The chapter presents basic principles of one-dimensional gas chromatography (1D-GC) and comprehensive two-dimensional gas chromatography (GC × GC) related to the main advantages of the two-dimensional technique, as well as its application to the study of organic compounds in liquids derived from coal, mainly through pyrolysis and extraction. It also shows the investigation of compounds contained in bio-oils obtained from biomass through pyrolysis, using GC × GC. Advances in scientific knowledge related to the composition of these complex matrices are shown through different examples of GC × GC analyses, such as the identification of trace compounds that would not be perceived by 1D-GC, organized patterns of elution of structurally related compounds that help their identification, etc. Examples shown make it clear that GC × GC is the technique of choice to elucidate composition of these complex matrices.