The reduction by hydrogen and the thermal decomposition of a siliceous nickel laterite ore in the presence of NaCl were studied using thermogravimetric analysis (TGA). Reduction tests on H2 atmosphere in rotary kiln were performed in the presence of NaCl and the product of the reaction was leached in ammoniacal solution. The presence of only 1 pct of NaCl in the furnace increased the nickel extraction values from ≈ 3 to ≈ 90 pct when the experiment was carried out at 850 °C. According to the results of X-ray diffractometry and TGA, the presence of NaCl in the system and the reducing atmosphere of H2 promote the segregation of nickel according to the following steps: (1) Nickel oxide reduction by hydrogen: NiO + H2(g) → Ni + H2O(g). (2) Formation of HCl: Al2SiO5 + 2NaCl + SiO2 + H2O → 2HCl(g) + 2NaAlSiO4. (3) Chlorination of metallic nickel by HCl: Ni + 2HCl(g) → NiCl2 + H2(g). (4) Reduction of nickel chloride by hydrogen: NiCl2 + H2(g) → Ni + 2HCl(g).