Abstract This work aimed to evaluate the detailed chemical structures of the asphaltenes in the tetrahydrofuran-microwave-extracted portions from two Chinese coals, namely, Shenfu and Zhundong coal (SF, ZD) and to clarify their characteristics on chemical composition at molecular level. Based on the analyses of diffuse reflectance Fourier transform infrared spectroscopy (DRIFT) and Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS), the detailed chemical structure of a series of basic and non-basic nitrogen- and oxygen-containing class species in the asphaltenes were clarified. The results revealed that condensed nitrogen-containing alkylaromatic structures with amidogens (1–3) were the main structure units in N 4 O y (y = 0–2) class species due to the high double bond equivalent (DBE) values for both the asphaltene from SF (A SF ) and the asphaltene from ZD (A ZD ). Acidic O 2 –O 7 class species with two or three aromatic rings were the main structure units, among which O 4 and O 2 class species had the highest relative abundances (RAs) in A SF and A ZD , respectively. Acidic oxygen-containing components in A ZD had narrower range of DBE and carbon number and mainly consisted of aromatic structure units with two rings. On the contrary, the average DBE values of O 4 –O 7 class species in A SF had positive relationship with oxygen atom number which could be attributed to the introduction of phenol groups. The results provided more detailed information on the structural characteristics of polar and aromatic-rich components of mobile phase in coal.