This paper examines the oxidation reaction of tert-amyl methyl ether (TAME), an oxygenated fuel additive, with chlorine radical initiators in the presence of oxygen. Data are collected at 298, 550, and 700 K. Reaction intermediates and products are probed by a multiplexed chemical kinetics synchrotron photoionization mass spectrometer (SPIMS) and characterized on the basis of the mass-to-charge ratio, ionization energy, and photoionization spectra. Branching fractions of primary products are obtained at the different reaction temperatures. CBS-QB3 computations are also carried out to study the potential energy surface of the investigated reactions to validate detected primary products.