Abstract Segregation of Rh in Ag-based alloys has been studied using the perturbed angular correlation of γ-rays emitted in the nuclear decay of radioactive 111In. The formation of impurity complexes, consisting of an 111In probe atom and one or more Rh atoms, was observed as a function of annealing time and temperature. Rhodium atom aggregation starts at about 600 K. From the fraction of 111In bound to isolated Rh atoms the solute rhodium atom concentration was determined. It increases with the nominal alloy concentration up to about 0.04 at.% and then it is essentially constant for the nominal Rh concentration varying between 0.1 and 0.5 at.%. The solute rhodium atom concentration is 3 times larger at the melting point than at 750 K.