We report the first direct observation of the decay of the excited-state population in electrons trapped on the surface of liquid helium. The relaxation dynamics, which are governed by inelastic scattering processes in the system, are probed by the real-time response of the electrons to a pulsed microwave excitation. Comparison with theoretical calculations allows us to establish the dominant mechanisms of inelastic scattering for different temperatures. The longest measured relaxation time is around 1 μs at the lowest temperature of 135 mK, which is determined by the inelastic scattering due to the spontaneous two-ripplon emission process. Furthermore, the image-charge response shortly after applying microwave radiation reveals interesting population dynamics due to the multisubband structure of the system.