Energy‐dispersive x‐ray fluorescence (EDXRF) spectrometry was used for the analysis of silicate rocks using pressed powder pellets. It is observed that with this low‐cost, simple and fast technique, trace elements such as V, Cr, Co, Ni, Cu, Zn, Ga, Pb, Th, Rb, Sr, U, Y, Zr and Nb can be determined along with 10 major oxides of Na, Mg, Al, Si, P, K, Ca, Ti, Mn and Fe with reasonably good accuracy and precision, depending upon the elemental abundance, analyte matrix and analytical conditions. Performance parameters such as minimum detection limit, accuracy and precision were estimated for these elements in silicate rocks under optimized analytical conditions. The technique is useful when a large number of samples are to be routinely analysed with sufficient accuracy and precision. Selection of operating parameters is discussed for the simultaneous analysis of several elements in a group. Copyright © 2000 John Wiley & Sons, Ltd.