Combustion is applied in industry, agriculture, transportation, and defenses et al., which at present provides most of our worldwide energy support. Human began to utilize combustion about one million years ago, and they studied the combustion about 150 years ago. In this review article, we introduce a new technique, synchrotron radiation vacuum ultraviolet single-photon ionization combining with molecular-beam mass spectrometry, applied to combustion study. The new method can detect the flame intermediates including stable and unstable species. Isomers can be distinguished with measuring photoionization efficiency spectrum (PIE). Thus, new compounds can be found even after 150 years of flame research, which can be helpful to develop kinetic model. Finally, some other applications are prospected with this new technique.