The present study reports on the performance of three reactor-produced radionuclides (24Na, 56Mn, and 72Ga) and one accelerator-produced radionuclide (56Co) for extending the full energy peak efficiency calibration of a coaxial HPGe detector up to ~3100 keV at different detector to source distance. The differences in the efficiency curves obtained with and without the use of high-energy gamma emitters radionuclides have a considerable impact on the accuracy of Na, Ca, and S determination by the k0-INAA as evidenced by analysis results of reference materials. The results revealed that the use of 24Na is the most suitable radionuclide for high-energy efficiency calibration due to its reasonable availability, low production cost, simple decay scheme, and well-defined decay properties.