γ-Ketohydroperoxide [3-(hydroperoxy)propanal] is an important reagent in synthetic chemistry and, in particular, oxidation reactions. It is considered to be a precursor for secondary organic aerosol formation in the troposphere. Due to enhanced reactivity and limitations associated with analytical techniques, theoretical methods have been employed to study the unimolecular reactivity of hydroperoxides. A number of automated reaction discovery techniques have been used to study the reactivity of γ-ketohydroperoxide, and a large number of reactions have been reported in such studies. In the present work, we have investigated the unimolecular reaction dynamics of this molecule using electronic structure theory calculations and direct chemical dynamics simulations to assess the relevance of different reaction pathways. Classical trajectories were launched from the reactant well with fixed amounts of total energies and integrated on-the-fly using density functional B3LYP/6-31+G∗ model chemistry. Three dissociation channels among the previously reported reactions were identified as important. Korcek decomposition, which was proposed earlier as a source of carbonyl compounds from thermal decomposition of γ-ketohydroperoxide, was not observed in the present high-temperature simulations. However, trajectories showed the formation of carbonyl compounds such as aldehydes via other pathways. Results are compared with previous studies, and detailed atomic-level reaction mechanisms are presented. © 2020 American Chemical Society.