Abstract For the purpose of empirical calibration of an ion microprobe, five synthetic silicate-glass standards having bulk compositions lying in or similar to compositions in the system diopside (CaMgSi 2 O 6)-albite (NaAlSi 3O 8)-anorthite (CaAl 2Si 2O 8) have been prepared. Each standard has been doped with 19 trace elements of geochemical importance. the trace-element concentrations ranging from 25 p.p.m. of each element to 500 p.p.m. per element by weight. These standards have been quantitatively documented for a number of trace elements by a variety of analytical techniques. In addition, data for eight natural clinopyroxenes (cpx) and 12 coexisting diopside-liquid pairs from equilibrium experiments in the system diopside-albite-anorthite (Di-Ab-An) have been used for calibration of secondary-ion intensity versus concentration. Calibration curves are presented for Na, Mg, Al, Ca, Ti, Se and Cr sputtered from cpx and glass, for Ba, Rb and Zr sputtered from glass, and for Fe sputtered from cpx. Mass interferences are suppressed by use of the energy-filtering technique of Shimizu et al. . The slopes of the working curves for these elements have been determined to within = 5–12% (1σ): correlation coefficients are typically better than 0.98. Although no simple theory explains the various slopes of the calibration lines, elements are preferentially sputtered from crystals. Therefore, glass standards cannot be used for trace-element analysis of crystals.