Understanding the thermal stability of intermetallic phases in Fe-rich Fe-Cr-Ni-Mo alloys is critical to alloy design and application of Mo-containing austenitic steels. Coupled with thermodynamic modeling, the thermal stability of intermetallic Chi and Laves phases in two Fe-CrNi-Mo alloys was investigated at 1273 K, 1123 K, and 973 K (1000°C, 850°C, and 700°C) for different annealing times. The morphologies, compositions, and crystal structures of the precipitates of the intermetallic phases were carefully examined by scanning electron microscopy, electron probe microanalysis, X-ray diffraction, and transmission electron microscopy. Two key findings resulted from this study. First, the Chi phase is stable at high temperature, and with the decreasing temperature it transforms into the Laves phase that is stable at low temperature. Secondly, Cr, Mo, and Ni are soluble in both the Chi and Laves phases, with the solubility of Mo playing a major role in the relative stability of the intermetallic phases. The thermodynamic models that were developed were then applied to evaluating the effect of Mo on the thermal stability of intermetallic phases in type 316 and NF709 stainless steels.