The volatilization of Ag from samples of complex composition by using various additives was investigated and the optimum conditions were established, viz., additive, Florisil-CaO ( 5 + 1-10 + 1 m/m); additive : sample mass ratio, 2; heating time, 2 h at 1200°C; and air flow-rate, 0.17 I min-1. The accuracy and precision of the method for the determination of Ag by flame atomic absorption spectrometry after separation by volatilization from copper tailings and a copper ore were found to be good.