Optical emission spectroscopy with high spatial resolution was applied for the study of plasma–material interaction in low-pressure reactive ion etching. Atomic and molecular emission by sputtered material has been found to be strongly localized near the surface. Excited particles are produced during sputtering by energetic ions, with the mechanisms being different for atoms and molecules. In atomic secondary photon emission, a cascade from highly excited levels is shown to be important. This method can be used as a probe during plasma processing. ©1997 American Institute of Physics.