The measurements of internal photoemission and photovoltage within the temperature range of 7–300 K have been performed for unannealed and annealed Au/n‐Si and Au/n‐GaAs samples. From the internal photoemission measurements, it was observed that annealing at different temperatures does not affect the relativity of interfacial Fermi‐level pinning to either the conduction band (for Au/GaAs) or the valence band (for Au/Si) but leads to a significant change of the Schottky barrier height. On the other hand, the photovoltage measurements show that the current transport at the metal/semiconductor interfaces is seriously affected by annealing. ©1995 American Institute of Physics.