Understanding the structure and composition of coals is important for effective, clean, and value-added utilization. In addition to gas chromatography=mass spectrometry which is commonly used to analyze coal, mass spectrometry (MS) may be used with other ion sources such as electrospray ionization (ESI) and direct analysis in real time (DART) for characterization. In this work, Geting bituminous coal was extracted sequentially and exhaustively with petroleum ether, carbon disulfide, methanol, acetone, an isometric acetone/carbon disulfide mixture, tetrahydrofuran, and an isometric tetrahydrofuran/carbon disulfide mixture. Raw coal, extracts, and the extraction residue were analyzed using MS equipped with ESI or DART. Organic heteroatomic species in the extracts were determined by liquid chromatography-mass spectrometry equipped with ESI. Molecular weight distributions of organic species in raw coal, extracts, and extraction residue were characterized by ESI-MS and DART-MS. Associated molecules and homologous compounds in coal extracts were identified.