The pyrolysis of tar-rich coal has become a research hotspot of clean and efficient utilization of coal, but there are still shortcomings in the difference of molecular structure characteristics of different maceral components. In order to deeply understand their structural characteristics and strengthen their theoretical basis. This study focuses on separating vitrinite and inertinite through equal density-gradient-centrifugation using Dabaodang coal from the Shenfu coal field. The enriched macerals were then analyzed using Fourier transform infrared spectroscopy (FTIR), solid-state nuclear magnetic resonance spectroscopy (13C-NMR), and X-ray diffraction spectroscopy (XRD). The 13C-NMR results indicated that the vitrinite-rich group had more aliphatic carbon structures, while the inertinite-rich group had more aromatic carbon structures. FTIR analysis revealed that the vitrinite-rich group had a higher concentration of oxygen-containing functional groups with shorter and highly branched aliphatic hydrocarbon structures, whereas the inertinite-rich group had benzene ring trisubstituents and pentasubstituents as the main aromatic hydrogens substitutions. The XRD results showed that the microcrystalline structures of both groups were similar with minimal differences in physical structures. The XPS results show that the oxygen-containing functional groups of vitrinite are mainly phenolic hydroxyl oxygen, ether oxygen and carboxyl oxygen, and the main forms of nitrogen are pyridine-type nitrogen and pyrrole type nitrogen, which provides a possibility for increasing the yield of pyrolysis tar. This study provides a comprehensive understanding of the molecular structure characteristics of macerals in low-rank bituminous coal from the Shenfu coal field, offering valuable insights for the development and utilization of tar-rich coal and the advancement of conversion technology.