<p>Vitrinite, is highly enriched in hydrogen, making it a crucial factor influencing tar-rich coal. However, the spatial variations in the tar yield of vitrinite remain unclear, and the impact of the coal-forming environment on its molecular structure requires further investigation. Therefore, this study investigated the tar yield, carbon structures, extractive composition, and coal-forming environment of vitrinite, aiming to reveal the influence of the coal-forming environment on tar yield and molecular structures. The results showed that due to variations in molecular structures, the tar yield of vitrinite varied across different regions and coal facies, with higher tar yield in limnic regions. Among them, VHT (vitrinite with high tar yield) exhibited more weak bonds, including <i>f</i>_<i>al</i>, <i>f</i>_<i>al</i>^<i>H</i>, <i>f</i>_<i>al</i>^<i>H</i>/<i>f</i>_<i>al</i>^<i>*</i>, <i>f</i>_<i>al</i>^<i>H</i>/<i>f</i>_<i>a</i>^<i>s</i>, <i>δ</i>, and <i>σ + 1</i>, which were positively correlated with tar yield. Conversely, the degree of condensation and branching (<i>f</i>_<i>a</i>, <i>X</i>_<i>bp</i>, <i>C</i>, <i>BI</i>) was negatively correlated with tar yield. Additionally, the small molecular compounds in VHT were lighter, showing a high main carbon number, low ΣC₂₁^-/ΣC₂₂⁺ ratio of n-alkanes, and low number of aromatic hydrocarbon rings. Moreover, the carbon structures and small molecular compounds in vitrinite were controlled by the coal-forming environment. These molecular structures were more closely related to coal facies parameters (tissue preservation index, vegetation index, and gelification index) in limnic than in wet forest swamp. This was because abundant herbaceous tissues in limnic regions were more prone to bacterial decomposition and gelation. Specifically, tissue preservation index and vegetation index had a greater impact on aliphatic chains, while the gelification index was more closely associated with the total content of aliphatic structure.</p>