Uniform and epitaxial NiSi2layers were obtained by consecutive irradiation of a Ni thin layer deposited onto Si with Nd‐glass laser irradiation, 30‐ns pulse duration, using up to 15 shots. The best quality epitaxial NiSi2layer, for a 50‐nm‐thick Ni layer deposited on Si(111), was obtained with 10 shots of 1.3 J/cm2energy density. The normalized minimum yield of the Ni signal amounted to 25%. The stability of the formed compound was investigated by furnace annealing in the 300–800 °C temperature range. After annealing at 300 °C‐1 h backscattering and channeling analysis indicated a worsening of the epitaxial quality of the compound. X‐ray diffraction patterns showed the presence of the NiSi silicide in addition to the NiSi2silicide. At 500 °C‐1 h annealing the reaction occurred over long distance and a large amount of NiSi was formed at the expense of the NiSi2and the unreacted Ni. At 800 °C the epitaxial quality of the NiSi2improved and the Ni minimum yield reached 10%. The NiSi2was the only silicide present after irradiation and 800 °C‐1 h annealing. Channeling analysis established also that the NiSi2wasbtype: i.e., the silicide layer was rotated 180° about the surface normal ⟨111⟩ axis of the Si substrate.