Chemical shifts of Si–Hx(x=1,2) species on Si surfaces obtained byexsituchemical treatment have been evaluated by high‐resolution x‐ray photoelectron spectroscopy at a take‐off angle of 5°. Optimizing the water rinse and sample loading conditions enables identification of the Si–Hxcomponents of the Si 2pcore‐level spectra, whose intensities display strong dependence on crystallographic orientation and surface treatment. NH4F‐treated Si(111) exhibits almost exclusive monohydride termination which induces a chemical shift of 250 meV relative to the bulk component. On the other hand, 4.5% HF‐treated Si(111) and 1% HF‐treated Si(100) surfaces show increased dihydride termination with an associated shift of 480 meV. ©1995 American Institute of Physics.