We theoretically investigated different thermal relaxation participating in the ultrafast thermionic emission processes on gold film surface with a femtosecond pulse excitation. The thermionic emission regimes under the two temperature relaxation and the thermal diffusion relaxation were demonstrated. The simulations showed that the thermionic emission properties can be defined in the regime under two temperature relaxation by reducing the laser fluence, or widening the pulse duration or increasing the laser wavelength. It was also found that there exists a transition between the two distinct thermionic emission regimes under peculiar laser parameters of laser fluence, pulse duration and laser wavelength. The results were explained as significant intervene of laser irradiation parameters into gold film thermal relaxation processes. (C) 2011 Elsevier B.V. All rights reserved.