Epitaxial type B NiSi2 thin layers have been grown at room temperature on Si(111). Deposition of a few monolayers of nickel followed by codeposition of NiSi2 has led to the growth of high quality single‐crystal layers, with ion channeling χmin ≪2%. No disorder was found at the interfaces of these layers. The topography of the original substrate has a predominant effect on the structure of line defects at the NiSi2 interface. Codeposition at room temperature on annealed silicide thin layers also led to the overgrowth of high quality NiSi2. These results are suggestive of type B NiSi2 formation on Si(111) upon deposition of a few monolayers of nickel at room temperature.