A semi‐empirical method was used in a full‐peak efficiency calculation procedure; it was based on the measurements of characteristic x‐ray lines of pure elemental and compound samples and on the application of the fundamental parameter method (FPM) for the theoretical calculation of the characteristic x‐ray intensities. Radioactive standards were applied for the efficiency calibration of different semiconductor detectors [Si(Li), Si‐PIN and HpGe]. The efficiency curves were fitted to the characteristic intensities measured by a conventional Si(Li) and two Si‐PIN detectors, using 125I and 55Fe radioactive sources for x‐ray excitation in a ring‐shaped geometrical arrangement. Several quantitative applications in x‐ and γ‐ray spectrometry were carried out with these calibrated detectors: (i) x‐ray fluorescence (XRF) analysis of sediment samples [Si(Li)], (ii) determination of specific activity of 137Cs nuclide in sediment core samples originated from an oxbow area of the river Tisza, using γ‐spectroscopy (HpGe) with low‐background conditions, (iii) study of electrosorption phenomena at solid– liquid interfaces by making use of an in situ radiotracer method based on the application of low‐energy x‐ray emitting radionuclides (e.g. 65Zn), (iv) quantitative XRF analysis of ceramic glaze and (v) electron microprobe analysis of aerosol particles using an instrument equipped with a thin‐window Si(Li) detector. Copyright © 2001 John Wiley & Sons, Ltd.