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For understanding of carrier behavior in semiconductors, it is important to measure the carrier relaxation time. In the present study, the relaxation times of inter-valley transition from the Γ valley to the X valley in GaP were evaluated by near-band-gap photoemission spectroscopy of electrons emitted from a surface with a negative electron affinity state. In the energy distribution curves, two peaks, which originate from the electron population accumulated in the Γ valley and the X valley, were observed. From the temperature dependence of the energy of these two peaks, we could successfully evaluate the temperature dependence of the energies of the Γ valley and the X valley. Furthermore, the relaxation times of the inter-valley transition from the Γ valley to the X valley were estimated from the ratio of the electron concentration of the Γ valley and the X valley. The values of the relaxation time are good agreement with the previous studies. These results indicate that the near-band-gap photoemission spectroscopy can directly investigate conduction electrons and also evaluate the carrier dynamics in semiconductor.