We discuss the trends in photoemission spectra from some silicon d-metal interfaces: Si (111)–Au, Si (111)–Ag, Si (111)–Ni, Si (111)–Pd, Si (111)–Pt. In particular, we discuss the correlation between the chemical processes taking place at the interface and those in the formation of bulk silicon d-metal compounds. Although a general correlation is found, some important differences are seen; in particular, no evidence of the formation of strictly stoichiometric silicides in the interface is found even for the cases in which well defined bulk silicides are known to be stable. We discuss also the role of the hybridization between d-electrons of the metal and (sp) electrons of silicon in the formation of intermixed interface phases. The considerations presented here can be useful as guidelines to interpret future results on other reactive silicon d-metal interfaces.