Extraction residue (ER) from Xianfeng lignite via ultrasonic extraction was subjected to methanolysis in the presence of NaOH at 300 degrees C for 2 h, and extracts 1-4 (E'(1)-E'(4)) from ER methanolysis were acquired by subsequent separation of the resulting soluble portion (SP). NaOH could promote ER methanolysis and hence increased the SP yield. Detailed molecular compositions (MCs) of E'(1)-E'(4) were characterized with Fourier transform infrared spectrometer, gas chromatograph/mass spectrometer (GC/MS), direct analysis in real time ionization source coupled to ion-trap mass spectrometer (DARTIS/ITMS), and atmospheric solid analysis probe/time of flight-mass spectrometer (ASAP/TOF-MS). The results show that the SP is rich in aliphatic moieties, carbonyl and hydroxy groups, and has molecular mass distribution ranging from m/z 100 to 600. According to GC/MS analysis, phenols, especially polymethylphenols, were enriched in E'(1) and E'(2), whereas almost all the alkanoic acids, alkanedioic acids, benzoic acids, and phenyl-substituted alkanoic acids only appeared in E'(4). A series of polar and/or involatile organic species, which are difficult to be detected with GC/MS, were detected with DARTIS/ITMS and ASAP/TOF-MS. NaOH could play an important role in cleaving ether bonds in ER during methanolysis and thereby enhanced the formation of oxygen-containing organic species. The use of multiple spectrometries provides a promising approach for understanding MC of the SP from coals. (C) 2014 Elsevier B.V. All rights reserved.