Abstract: Combustion is the main energy source in the world, and plays an important role in the fields of transportation, industrial production, aerospace, etc. The combustion process is accompanied by the production of pollutants, which lead to serious environmental problems. In order to improve combustion efficiency and reduce pollutant emissions, it is necessary to understand and control combustion. As intermediates are the chain nodes of combustion reaction network, qualitative and quantitative measurements of key intermediates are essential not only for understanding combustion, but also for developing and verifying combustion reaction kinetic models. On the other hand, the preparation of various chemicals and fuels involves catalytic processes. The detection of catalytic reaction intermediates can further reveal the catalytic reaction mechanism, regulate the catalytic reactions and improve the conversion of target products. The detection of these key intermediates, especially active intermediates, has always been challenging. In recent years, the synchrotron radiation vacuum ultraviolet photoionization mass spectrometry (SVUV PIMS) combined with molecular beam sampling, can detect the key intermediates in the process of combustion and catalytic reaction, such as enols, hydroperoxides, free radicals, etc. Herein, SVUV PIMS and its application in combustion and catalysis were summarized in detail, and the future development direction was prospected.