AbstractSulfide alkoxy radicals are important intermediates during the partial oxidation of alkyl sulfides in atmospheric chemistry and in combustion. The atmospheric reaction sequence to formation of the alkoxy radicals includes (1) initial reaction with OH to create a radical on a carbon site, (2) the carbon radical then associates with 3O2 to form a peroxy radical, and (3) an NO radical reacts with the peroxy radical to form an alkoxy radical (RO•) plus NO2. This study determines structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (ΔfH°, S°, and Cp(T)) of 3 corresponding alcohols HOCH2SCH2CH3, CH3SCH(OH)CH3, and CH3SCH2CH2OH of methyl ethyl sulfides studied in order to characterize the thermochemistry of the respective alkoxy radicals. The lowest energy molecular structures were calculated using the B3LYP density functional level of theory with the 6‐311G(2d,d,p) basis set. Standard enthalpies of formation (ΔfH°298) for the radicals and their parent molecules were calculated using B3LYP/6‐31 + G(2d,p), CBS‐QB3, M062x/6‐311 + g(2d,p), and G3MP2B3 methods. Isodesmic reactions were used to determine ∆fH° values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31 + G(d,p) level theory. The contributions for S°298 and Cp(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by CBS‐QB3 calculations, with contributions from torsion frequencies replaced by internal rotor contributions. Group additivity and hydrogen bond increment values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxide molecules and their radicals.