||The solubilities of rhodium (Rh) in a molten silver alloy in doré-smelting conditions for treating copper refinery slime at temperatures of 1,000 to 1,300 °C were measured using a high-temperature equilibration-quenching technique and direct phase analysis by electron probe X-ray microanalysis. The results obtained indicate that the solubility of rhodium in molten silver is very limited: only 0.04 to 0.26 weight percent at 1,000 and 1,300 °C, respectively. The thermodynamic properties of rhodium in molten silver were estimated from the solubility data. The compositions of the solid rhodium alloys in equilibrium with molten silver-rich doré metal were also measured in this study. The excess rhodium in the doré alloy will precipitate during the refining as solid, greater than 99 weight percent Rh.