Abstract: Shendong Shangwan coal (SDR) and its inertinite concentrated(SDI)from petrographical separation were characterized by ¹³C-CP/MAS NMR, FT-IR and XPS and their structure unit information was obtained. Based on structure parameters and elemental analysis, macromolecular structure models of SDR and SDI were constructed and ¹³C chemical shift of the two models was calculated by ACD/CNMR predictor. The results indicate that naphthalene with condensation degrees of 2 is the main form of aromatic carbon in SDR, naphthalene and phenanthrene are those in SDI. The aromaticity of SDI is greater than that of SDR. For SDR and SDI, oxygen atoms are present as carbonyl groups and nitrogen atoms exist in the forms of pyridine and pyrrole. The calculated chemical shift spectrogram of model is well consistent with that of the experimental results. The structural formulas calculated for SDR and SDI are C₁₈₁H₁₃₆N₂O₂₄ and C₁₈₆H₁₄₈N₂O₂₂, respectively.