Molecular-beam sampling mass spectrometry (MBMS) combined with tunable synchrotron radiation photoionization technique offers obvious advantages for the study of flame chemistry over other techniques because of the precision measurement of the combustion intermediates and products in flame. In this paper, the results to identify combustion intermediates in low-pressure premixed gasoline/oxygen flame with the synchrotron radiation were reported. Based on the results obtained, the formation process of five products and the difference between gasoline/oxygen and MTBE/gasoline/oxygen flame were emphatically analyzed. The results achieved provide data basis for the analysis of intermediates and radicals in flame, and are helpful to establish the kinetic modeling of gasoline/oxygen and MTBE/gasoline/oxygen flames.