Nanocrystalline alloys often show exceptional thermal stability as a consequence of kinetic and thermodynamic impediments to grain growth. However, evaluating the various contributions to stability requires detailed investigation of the solute distribution, which is challenging within the fine structural-length-scales of nanocrystalline materials. In the present work, we use a variety of techniques to assess changes in the grain size, chemical ordering, grain-boundary segregation, and grain-boundary structure during the heat treatment of Ni–W specimens synthesized over a wide range of grain sizes from 3 to 70 nm. A schematic microstructural evolution map is also developed based on analytical models of the various processes activated during annealing, highlighting the effects of alloying in nanocrystalline materials.