The Pd-Rh phase diagram has been reinvestigated in the subsolidus region using X-ray diffraction, scanning and transmission electron microscopy. The true equilibrium at the miscibility boundary was achieved with the two-way approach. Nanosized powders of metastable solid solutions and two-phase palladium-rhodium mixtures were used to shorten the time required to equilibrate the system. The initial samples were prepared by decomposition of coordination compounds [Pd(NH3)2Cl2], [Rh(NH3)5Cl]Cl2, [Pd(NH3)4]3[Rh(NO2)6]2and [Pd(NH3)4][Rh(NH3)(NO2)5]. The obtained phase diagram exhibits miscibility gap wider than generally accepted with the critical point of solubility at 58 at.% Rh and 820 °C.