Abstract: The conversion and utilization are fundamentally determined by the chemical composition of coal. The establishment and simulation of coal molecular model can reduce the experimental cost and experimental time, and improve the research efficiency. However, the chemical composition of coal exhibited significant complexity due to the complex coal−forming plants and depositional environments. Therefore, the accurate construction of coal molecular models, which can truly reflect the physical and chemical properties of coal, is essential for the research of clean and efficient utilization of coal. In this study, the coal slime from Pingshuo mining area in Shanxi Province was used as the research object. The relative contents and specific chemical states of carbon (C), oxygen (O), and nitrogen (N) were analyzed by 13C nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and X−ray photoelectron spectroscopy (XPS). The results showed that Pingshuo coal slime does not contain any aromatic methyl groups. The carbon element mainly exists in the chemical form of mono− and polycyclic aromatic carbons. The oxygen element mainly exists in chemical forms such as ester group and hydroxyl group. The nitrogen element mainly exists in the chemical form of pyridine compounds. Based on the chemical analysis structure, the molecular model of Pingshuo coal slime was constructed. The molecular model of C₁₃₆H₁₅₀O₁₈N₂ was optimized by molecular simulation method, and the correctness of the model was verified by ¹³C NMR spectral line prediction verification and density verification. The ¹³C NMR spectrum prediction and density verification results showed that the model spectral line is in good agreement with the measured spectral line, and the difference between the model density and the actual density of coal is only 0.019 g/cm³, indicating that the model is well representative. This research provides a crucial molecular−level understanding of the coal's chemical architecture and establishes a robust theoretical foundation for developing efficient and clean coal conversion technologies.