Determination of the full-energy peak efficiency of a detection system is significant in the activity calculation of the measured radioactive samples. In this work, we present an experimental method to determine the absolute efficiency calibration of a NaI(Tl) detector, considering that a standard source of interest is unavailable and by using the known specific activity of a standard sample measured using a HPGe detector. The efficiency of a gamma-ray spectrometer that consists of a coaxial HPGe detector is calculated using Canberra ISOCS/LabSOCS software and a fabricated calibration source. To validate our method, environmental samples (rock and soil samples) were analyzed on both the detectors. The obtained activity concentrations were checked by means of the IAEA proficiency test procedure. The performance criteria evaluation results were found to be ‘Acceptable’ for all the analytical determinations of all the radionuclides under study, except for the samples with low activity (<15 Bq kg−1 and <10 Bq kg−1 for 226Ra and 232Th, respectively). The precision of the low-activity samples was not considered ‘Acceptable’ as the results were slightly inaccurate; in this case, the results were considered as ‘Warning’ because the relative bias (RB) was less than the maximum acceptable bias (MAB).