Detailed characterization of organic components in low-rank coals is essential for the utilization of coals in clean, effective and value-added ways. Two kinds of low-rank coals were subjected to sequential thermal dissolution in the order of cyclohexane, acetone, and methanol to obtain six soluble portions (SPs) from the coals. Two gas chromatographic systems, gas chromatography/mass spectrometry (GC/MS) and comprehensive two dimensional gas chromatography/time-of-flight mass spectrometry (GCxGC/TOF MS), were applied to the characterization of the SPs. Compared to GC/MS, a routine analytical technique for complex mixtures, GC x GC/TOF MS improves the separating power, overcomes the co-elution, and reveals more structural details in complex mixtures like coals. Low-polar compounds like aliphatic hydrocarbons and arenes tended to be extracted by cyclohexane. High content of polar alcohols and phenols were identified in the SPs of methanol. Acetone could enrich nitrogen-containing organic compounds (NCOCs) due to hydrogen bond of N-H...O between NCOCs and acetone. Additionally, a series of low-concentration species including some isomers in the SPs were only identified by GC x GC/TOF MS. Distributions of various classes of compounds on the two-dimensional total ion chromatograms plot were discussed according to the separation mechanism of the two columns. Detailed analysis of biomarkers was also exhibited and discussed.