Understanding the molecular composition of oxygen-containing aromatics (OCAs) in low-temperature coal tar (LTCT) is of great importance for separating value-added chemicals from LTCT and catalytically hydrogenating LTCT. Herein, petroleum ether and CH3OH were used to enrich OCAs from a LTCT. The OCAs were analyzed with a Fourier transform infrared spectrometer (FTIRS), gas chromatograph/mass spectrometer (GC/MS), and quadrupole exactive orbitrap mass spectrometer (QEOTMS) with electrospray ionization source in negative-ion mode (NIM). As a result, -OH group proved to be the most abundant oxygen-containing group in the LTCT. The m/z values of OCAs detected with QEOTMS mainly range from 150 to 350 in NIM. The main OCAs detected in the LTCT are O-1-O-3 class species with double bond equivalent (DBE) values and carbon numbers (CNs) ranging from 1 to 16 and 6 to 28, respectively. After extraction, most of the arenols are transferred into lower phase 2 (LP2). The main OCAs detected in LP2 are O-1 -O-3 class species with DBE values and CNs ranging from 1 to 14 and 6 to 25, respectively. After catalytic hydroconversion, neither unsaturated hydrocarbons (USHCs) nor OCAs were detected with GC/MS, while a handful of OCAs were identified with QEOTMS, indicating that all the USHCs and most of the OCAs in the LTCT were hydroconverted to alkanes and that QEOTMS is more effective for identifying OCAs, including strongly polar and/or less volatile OCAs in LTCT.