With cyclohexane (CH), benzene (BE), and ethyl acetate (EA) as solvents, Naomaohu lignite (NL, a typical oil-rich, low-rank coal) from Hami, Xinjiang, was thermally dissolved (TD) to obtain three types of soluble organics (NLCH, NLBE, and NLEA) and the corresponding insoluble portions (NLCH-R, NLBE-R, and NLEA-R). Ultimate analysis, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG-DTG), and gas chromatography-mass spectrometry (GC/MS) were used to characterize NL and its soluble and insoluble portions. Results showed that, compared with NL, the C element in NLCH-R, NLBE-R, and NLEA-R increased, while the O element decreased significantly, indicating that thermal dissolution is a carbon enrichment process and an effective deoxidation method. The GC/MS results showed that oxygen-containing organic compounds (OCOCs) are dominant in NLCH, NLBE, and NLEA. NLCH is mainly composed of ketones (11.90%) and esters (19.04%), while NLBE and NLEA are composed of alcohols (12.18% and 2.42%, respectively) and esters (66.09% and 84.08%, respectively), with alkyl and aromatic acid esters as the main components. Among them, EA exhibits significant selective destruction for oxygen-containing functional groups in NL. XPS, FTIR, and TG-DTG results showed that thermal dissolution can not only affect the macromolecular network structure of NL, but also improve its pyrolysis reactivity. In short, thermal dissolution can effectively obtain oxygen-containing organic compounds from NL.