In this work the interface between transition metals (Fe, Co) and Si has been investigated by soft X-ray photoemission spectroscopy. Synchrotron radiation has been used as photon source, measuring valence bands, Si2p and metal 3p core levels with high surface sensitivity. CoSi2 and beta-FeSi2 chemical phases have been obtained by thermal annealing (500-800-degrees-C) of thin films deposited onto room temperature Si<111> and <100> oriented wafers. Moreover, for the first time to our knowledge, a mixed (Fe0.785-Co0.25)/Si multilayered interface has been studied, showing remarkable differences with respect to single-metal deposition.