Chemical bonding at the interface of a near-noble-metal (Ni) and a transition metal (Cr) with Si is examined through synchrotron radiation photoelectron spectroscopy studies of in situ formed interfaces, of cleaved bulk silicides, and of disordered surfaces prepared by sputter etching of the silicides. Interpretation of these experimental results is guided by parallel linear combination of atomic orbitals (LCAO) (extended Huckel approximation) calculations of stoichiometric Ni and Cr silicides.