The initial stage of silicide formation at the Pd/Si interface has been investigated during Pd deposition on the Si(111) surface using a combination of AES and TEM techniques. The formation of silicide was found to change the valence state of Si significantly as observed from the shape change of the SiLVVAuger spectra. The ratios of the normalized peak intensities were used to calibrate the composition and the thickness of the reacted layer. The calibration results coupled with TEM phase identification showed uniform formation of the Pd2Si compound even at room temperature up to about 10 Å Pd coverage. Using thin Pd coverages of about 10 Å, epitaxial growth of Pd2Si was not observed on sputter‐cleaned Si surfaces. Crystalline order was clearly observed at the Pd2Si/Si interface in annealed samples with less than 4 Å Pd2Si, indicating a relatively sharp interface with no significant amorphous‐like structural disorder.