We present synchrotron radiation photoemission results from Si(111) with increasing Pd coverages ϑ (in monolayer units from 0.5 to 23 monolayers). We have measured photoemission spectra in the Cooper minimum for the Pd 4d electrons (hν = 130 eV) and outside this region (hν = 80 eV) where the d emission in strong. By comparing the two cases, one obtains information on the Si (sp) and Pd (d) states. Making use of this, we discuss in detail the coverage dependence of the spectra in connection with the nature of the chemical bond between Si and Pd and the structure of the Si–silicide interface.