The mercury-photosensitized oxidation of isobutane has been studied over a wide range of pressures of the hydrocarbon and oxygen, in a conventional static photochemical apparatus at the temperatures of 30 °C and 100 °C. The main products of the reaction are tertiary butyl hydroperoxide, together with tertiary butyl alcohol, acetone, and corresponding small quantities of formaldehyde and methyl alcohol. Isobutyraldehyde was also detected; ditertiary butyl peroxide being notably absent. Peroxide yields suggest that a reaction between an excited isobutane molecule and oxygen is important in the initiation processes and that peroxide is formed in the reaction[Formula: see text]