Gasoline fuels are complex mixtures that vary in composition depending on crude oil feedstocks and refining processes. Gasoline combustion in high-speed spark ignition engines is governed by flame propagation, so understanding fuel composition effects on premixed flame chemistry is important. In this study, the combustion chemistry of low-pressure, burner-stabilized, premixed flames of two gasoline fuels was investigated under stoichiometric conditions. Flame speciation was conducted using vacuum-ultraviolet synchrotron photoionization time-of-flight molecular beam mass spectroscopy. Stable end-products, intermediate hydrocarbons, and free radicals were detected and quantified. In addition, several isomeric species in the reaction pool were distinguished and quantified with the help of the highly tunable synchrotron radiation. A comparison between the products of both flames is presented and the major differences are highlighted. Premixed flame numerical simulations were conducted using surrogate fuel kinetic models for each flame. Furthermore, a new approach was developed to elucidate the main discrepancies between experimental measurements and the numerical predictions by comparing quantities of interest. © 2016.