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Evidence is presented for a significant influence of electrode surface material and condition on the measurement of the kinetic energies of ions sampled from discharges through an orifice in the electrode. Significant differences in ion energy shifts and/or discrimination of low‐energy ions are found using aluminum and stainless‐steel electrodes in a radio‐frequency (rf) discharge cell. It is argued that the observed differences in energy shifts may be attributable in part to differences in charging of oxide layers on the electrode surface around the sampling orifice. © 1995 American Institute of Physics.