To extend the rule‐based approach for hydrogen abstraction reactions from oxygenated compounds, a systematic investigation was performed to examine the reactivity of gas‐phase hydrogen abstraction reactions from alkyl groups (methyl and ethyl groups) bound to oxygen atoms in five types of oxygenated compounds (alcohols, ethers, formate esters, acetate esters, and carbonate esters) by H atoms and HO2 radicals comprehensively considering rotational conformers. Quantum chemical calculations were conducted at the CBS‐QB3 level for stationary points. Rate constants were determined employing conventional transition state theory (TST). For hydrogen abstraction reactions by H, the rotational conformer distribution partition function was employed to approximate partition functions, owing to the similarity in vibrational energy‐level structures among conformers. In hydrogen abstraction reactions by HO2, the vibrational structures of transition‐state (TS) conformers varied significantly due to the hydrogen bonding, leading to an inappropriate evaluation of rate constants when using the lowest‐energy conformer as a representative. Therefore, the rate constants were calculated by the multi‐structural TST. It was revealed that the differences in functional groups containing O atoms mainly affect the bond dissociation energies of the C–H bonds and the activation energies of hydrogen abstraction reactions only when the C atoms are adjacent to the O atoms. Additionally, it was found that hydrogen bonds formed in the TSs show minor effect on rate parameters for the overall rate constants, apart from the reduction of the pre‐exponential factors for the H‐abstraction reactions from the methylene position of ethyl groups. The comparison with the rate constants from previous studies showed reasonable results, indicating that the rate constants in this study, which thoroughly consider rotational conformers, can be the current best estimates.