Energy dispersive X‐ray fluorescence (EDXRF) analyses are compared with neutron activation as well as atomic absorption analyses of ancient copper‐based alloys in order to examine their accuracy and to estimate realistic values for precision and sensitivity of EDXRF. The results show that it is possible to obtain reliable data of the surface composition of objects non‐destructively. Better results for bulk composition are usually obtained with drill samples where the sensitivity of the method is at least competitive with atomic absorption spectroscopy with flame atomization.