X-ray photoelectron spectroscopy using synchrotron radiation has been used to investigate the HfO2/SiO2 interface chemistry of high-quality 0.6 and 2.5 nm HfO2/0.6 nm SiO2/Si structures. The high energy resolution (0.15 eV) along with the high brightness level allows us to separate, unambiguously, on both Hf 4f and Si 2p core-level spectra, interfacial Hf–silicate bonds from bulk HfO2 and SiO2 contributions, thus making possible subsequent quantitative treatments and modeling of the interfacial layer structure. Careful assessment of the energy shift of the interfacial components shows that Si-rich Hf silicates are present. The underlying assumption that initial-state contribution dominates the observed Si 2p shift is briefly discussed. © 2002 American Institute of Physics.