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Accurate thermochemical data are of great importance in developing quantitatively predictive reaction mechanisms for transportation fuels, such as diesel and jet fuels, which are primarily composed of large hydrocarbon molecules, especially large straight-chain alkanes containing more than 10 carbon atoms. This paper presents an ONIOM[QCISD(T)/CBS:DFT]-based theoretical thermochemistry study on the hydrogen abstraction reactions of straight-chain alkanes, <i>n</i>-C_nH_2n+2, (<i>n</i> = 1–16) by hydrogen (H), hydroxyl (OH), and hydroperoxyl (HO₂) radicals. These reactions, with <i>n</i> ≥ 10, pose significant computational challenges for prevalent high-level ab initio methods. However, they are effectively addressed using the ONIOM-based method. One notable aspect of this study is the consideration of the high symmetry of straight-chain alkanes. This symmetry allows us to study half of the reactions, employing a generalized approach. Therefore, a total of 216 reactions are systematically studied for the three reaction systems. Our results align very well with those from the widely accepted high-level QCISD(T)/CBS method, with discrepancies between the two generally less than 0.10 kcal/mol. Furthermore, we compared large straight-chain alkanes (<i>n</i>-C₁₆H₃₄ and <i>n</i>-C₁₈H₃₈) with large methyl ester molecules (C₁₅H₃₁COOCH₃ and C₁₇H₃₃COOCH₃) to elucidate the impact of functional groups (ester group and C=C double bond) on the reactivity of the long-chain structure. These findings underscore the accuracy and efficiency of the ONIOM-based method in computational thermochemistry, particularly for large straight-chain hydrocarbons in transportation fuels.