An x-ray photoelectron spectroscopy system with a laser-plasma x-ray source is shown to have energy resolution high enough to observe chemical shifts ofSi 2pelectrons inSiO2,Si3N4,and pure Si. A boron nitride (BN) plasma x-ray source is produced by irradiation of 100 mJQ-switched YAG laser pulses. A single line emission at 4.86 nm is selected from the BN plasma by means of carbon foils. Fine spectra are acquired with only 96 laser shots. The results obtained confirm that a laboratory-sized x-ray photoelectron spectroscopy system with submicron spatial resolution and high spectral acquisition speed can be realized. ©1998 American Institute of Physics.