Copper refinery anode slimes are abundantly produced during the electrolytic refining of copper. Although the slimes contain significant and economically recoverable amounts of gold and silver, the chemical state of the gold has not been fully identified. In the present work, the chemical form of gold in a copper anode, in a raw slime, and in slimes treated by different leaching procedures has been investigated by Mossbauer spectroscopy with the 77.3 keVγ-rays of197Au. The Mossbauer spectrum of the anode is typical of a dilute Au:Cu alloy. The spectrum of the raw slime consists of two components, namely, a single, rather broad line with an isomer shift (IS) of about −0.3 mm/s relative to a Pt metal source and a quadrupole doublet with an IS of + 1.2 mm/s and a quadrupole splitting of 5.0 mm/s. The single line component can be attributed to a gold-rich alloy, with an approximate composition of Au60Ag{n40} or Au80Cu20 if it is a binary alloy, or to a ternary Au-Ag-Cu alloy of appropriate composition. The parameters of the quadrupole doublet match those of Ag3AuSe2 (fischesserite) or related Ag2−xAuxSe compounds. In these compounds, the gold atoms are coordinated by two selenium atoms in a linear arrangement, as is typical for Au(I). It was found that the ratio between the concentrations of the metallic phase and the selenide strongly depends on the leaching conditions. The measurement of the Lamb-Mossbauer factor of fischesserite is also reported.