Soluble portions (SPs) 1–4 (SP1–SP4) were afforded from sequentially dissolution and alkanolyses of Baiyinhua lignite (BL) in cyclohexane, CH3OH, CH3CH2OH, and (CH3)2CHOH at 300 ℃. They were analyzed with a gas chro-matograph/mass spectrometer and quadrupole exactive orbitrap mass spectrometer (QEOTMS) with an atmo-sphere pressure chemical ionization source in positive-ion mode, while BL was characterized with an X-ray photoelectron spectrometer (XRPES). The results show that the yields of SP2 and SP3 are much higher than those of SP1 and SP4, and the total SP yield is ca. 39.0％. According to the analysis with XRPES, pyrrolic nitrogen atoms are the most abundant nitrogen existing forms in BL. Thousands of nitrogen-containing aromatics (NCAs) were resolved with QEOTMS and their molecular masses are mainly in the range of 200–450 u. The main NCAs are N1O1 and N1O2 class species with double bond equivalent values of 4–18 and carbon numbers of 7–30. The nitrogen atoms appear in pyridines, quinolines, benzoquinolines or acridine, and dibenzoquinolines or naphthoquinolines, while the oxygen atoms exist in methoxy and furan rings.