Abstract Baiyinhua lignite (BL) was sequentially treated in cyclohexane, CH3OH, CH3CH2OH, and (CH3)2CHOH at 300 °C to afford soluble portions (SPs) 1–4 (SP1–SP4), which were analyzed with a Fourier transform infrared spectrometer, gas chromatograph/mass spectrometer (GC/MS), and quadrupole exactive orbitrap mass spectrometer (QEOTMS) with atmosphere pressure chemical ionization source in negative-ion mode. In addition, it was characterized with a solid-state 13C nuclear magnetic resonance and X-ray photoelectron spectrometer (XRPES). The results show that aliphatic and aromatic carbons, accounting for 37.1% and 59.2%, respectively, are dominated in BL. Each aromatic cluster contains 2 rings on average with 3 substituent groups on each ring. According to the analysis with XRPES, –OH group is the most abundant existing form of oxygen in BL. The analysis with GC/MS shows that the most abundant group components are arenols in SP1 and SP2, and alkanoates in SP3. Thousands of oxygen-containing aromatics (OCAs) were resolved with the QEOTMS and the molecular masses are mainly in the range of 250–400 μ. The main OCAs detected are O1–O6 class species, dominated by O2–O5 class species, which could be mainly assigned to acidic species, such as alkylarenediols, alkylarenetriols, and alkylarenoic acids.