AbstractA crucial chain‐branching step in autoignition is the decomposition of ketohydroperoxides (KHP) to form an oxy radical and OH. Other pathways compete with chain‐branching, such as “Korcek” dissociation of γ‐KHP to a carbonyl and an acid. Here we characterize the formation of a γ‐KHP and its decomposition to formic acid+acetone products from observations of n‐butane oxidation in two complementary experiments. In jet‐stirred reactor measurements, KHP is observed above 590 K. The KHP concentration decreases with increasing temperature, whereas formic acid and acetone products increase. Observation of characteristic isotopologs acetone‐d₃ and formic acid‐d₀ in the oxidation of CH₃CD₂CD₂CH₃ is consistent with a Korcek mechanism. In laser‐initiated oxidation experiments of n‐butane, formic acid and acetone are produced on the timescale of KHP removal. Modelling the time‐resolved production of formic acid provides an estimated upper limit of 2 s⁻¹ for the rate coefficient of KHP decomposition to formic acid+acetone.