Gold and iron are known to interact in silicon at temperatures below ∼400 °C to form gold‐iron pairs with band‐gap energy levels ofEv+0.434 eV andEc−0.354 eV. In this work, the details of the formation and dissociation of these pairs were examined and from the equilibrium concentrations a binding energy of 1.22±0.02 eV was deduced. The activation energy of the gold‐iron pair formation process was found to be 0.8 eV; when corrections were made to extract the activation energy for the iron diffusion coefficient from the data, a value of 0.42 eV was obtained. This is substantially smaller than the values of 0.7–0.9 eV obtained from iron precipitation and iron‐boron pairing studies. It was noted during the higher‐temperature dissociation process that there was concurrent precipitation of the iron which caused the dissociation to appear to be a two‐stage process. This precipitation also resulted in substantial irreversibility of successive dissociation and pair formation anneals. Finally, it is pointed out that these low‐temperature instabilities in the concentration of gold and the deep‐level gold‐iron complex are likely to result in device instabilities when gold and iron contamination occur.