Alkanes with one or more methyl substitutions are commonly found in liquid transportation fuels, so a fundamental investigation of their combustion chemistry is warranted. In the present work, stoichiometric low-pressure (20 Torr) burner-stabilized flat flames of 2-methylheptane and 3-methylheptane were investigated. Flame species were measured via time-of-flight molecular-beam mass spectrometry, with vacuum-ultraviolet (VUV) synchrotron radiation as the ionization source. Mole fractions of major end-products and intermediate species (e.g., alkanes, alkenes, alkynes, aldehydes, and dienes) were quantified axially above the burner surface. Mole fractions of several free radicals were also measured (e.g., CH3, HCO, C2H3, C3H3, and C3H5). Isomers of different species were identified within the reaction pool by an energy scan between 8 and 12 eV at a distance of 2.5 mm away from the burner surface. The role of methyl substitution location on the alkane chain was determined via comparisons of similar species trends obtained from both flames. The results revealed that the change in CH3 position imposed major differences on the combustion of both fuels. Comparison with numerical simulations was performed for kinetic model testing. The results provide a comprehensive set of data about the combustion of both flames, which can enhance the erudition of both fuels combustion chemistry and also improve their chemical kinetic reaction mechanisms.