Two methods have been developed for the determination of platinum group elements (PGEs) and gold in four geological reference materials: one using radiochemical neutron activation analysis and the other using nickel sulphide fire assay, followed by instrumental neutron activation analysis. The results from ten multiplicate measurements have been discussed in terms of precision and accuracy. The average precision for both methods is about 5%. Comparing the reported data with existing values in the literature, the accuracy of the proposed methods is good agreement in most cases. Detection limits in the range 0.001–0.015 ng have been derived for both methods under the operational conditions.