High-level electronic structure calculations were carried out for the study of the reaction pathways in the OH-initiated oxidations of methyl vinyl ketone (MVK) and methacrolein (MACR). For the two conformers of MVK (called synperiplanar and antiperiplanar), the addition channels of OH to the terminal and central carbon atom of the double bond dominate the overall rate constant, whereas the abstraction of the methyl hydrogen atoms has no significant kinetic role. In the case of MACR, only the antiperiplanar conformer is important in its reactivity. In addition, the lower Gibbs free energy barrier for MACR corresponds to the aldehydic hydrogen abstraction reaction, which will be somewhat more favorable than the addition processes. The subtle balance between the different pathways (additions versus abstractions) serves to give an understanding of the pressure dependence of the rate constants of these tropospheric oxidation processes.