Methanol-to-olefins (MTO) is a very important industrial catalysis technique for the production of light olefins, which is of great economic value and strategic significance. However, it is a great challenge for the traditional analytical methods to obtain the real-time information of product variation during MTO reaction process, which is vital for the conversion process research and mechanism explanation. In this study, a single photon ionization time-of-flight mass spectrometry (SPI-TOFMS) based on a windowless RF-discharge (WLRF) lamp was developed for real-time measurement of catalytic product during the initial stage of MTO reaction. The vacuum ultraviolet (VUV) photon energy was easily adjusted by changing the discharge gas. Argon (Ar) gas was eventually adopted as the discharge gas, since it produces photons with appropriate energy of 11.6 eV and 11.8 eV for ionization of light olefin molecules. The detection sensitivities of ethylene and propylene were largely improved to a substantially similar level with limits of detection (LODs) down to 16.98 and 9.64 ppbv, respectively. The initial stage of MTO reaction was real-time monitored with a high temporal resolution of 0.5 s, revealing that ethylene was the first olefin product followed by propylene. The successful application of WLRF-SPI-TOFMS in the monitoring of MTO catalytic process indicated broad application prospects of this instrument in the industrial reaction process monitoring.